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Advanced Inorganic Chemistry Oct. 9 – Dec. 25 Prof. Lu Jun [email protected], School of Science, State Key Laboratory of Chemical Engineering Huaxin Building , 204B Chapter 3 Coordination chemistry Aims and demands Stereoisomerism of coordination compounds Basic theory of chemical bonds of coordination compounds (crystal field theory、ligand field theory) Reaction mechanism and kinetics characteristics of coordination compounds New functional coordination compounds contents 1. Basis of coordination chemistry 2. Coordination stereochemistry 3. Coordination chemistry theory 4. Reaction mechanism of complex 5. New functional coordination compounds Section 1 Basis of coordination chemistry 1.1 History and development of coordination chemistry 1.2 Definition of coordination compounds and nomenclatue 1.3 Basic types of ligand and coordination ability 1.4 Classification of the coordination compounds Section 1 Basis of coordination chemistry 1.1 History and development of coordination chemistry In the 18th century (in 1704), the earliest record of the coordination compounds in literature: Fe4[Fe(CN)6]3 (prussian blue) During the chinese ancient Zhou dynasty (1045 -221B.C.): Synthesized red alizarin dye by madder root and clay/alumen Red coordination compounds contains Al3+, Ca2+ Section 1 Basis of coordination chemistry 1.1 History and development of coordination chemistry In 1893, Swiss chemist Alfred Werner(26), published a famous paper: 1) the basic conception: modern coordination bond, coordination number, structure of coordination compounds, 2) clarifying space configuration and isomerism of coordination compounds using idea of stereochemistry. 3) the foundation of coordination chemistry, and marked the establishment of coordination chemistry discipline. Section 1 Basis of coordination chemistry 1.1 History and development of coordination chemistry Many Nobel Prize winners associated with coordination chemistry: 1913, Werner: Creating the coordination chemistry 1955, Ziegler and Natta: Metal olefin catalysts 1967, Eigen: Rapid response 1971, Lipscomb: Borane theory 1973, Wilkinson and Fischer: Developing organometallic chemistry 1982, Hoffmann: Isolobal theory 1983, Taube: Electron transfer mechanism of complexes 1987, Cram, Lehn and Pedersen: Supramolecular chemistry 1992, Marcus: Electron transmission theory Section 1 Basis of coordination chemistry 1.1 History and development of coordination chemistry Development direction of coordination chemistry: Synthesis and structural characterization of new functional coordination compounds; Completeness and development of coordination chemistry theory; For biological sciences, form bioinorganic chemistry; For material sciences, form molecular functional materials; For supramolecular chemistry, structure molecular devices. Section 1 Basis of coordination chemistry 1.2 Definition of coordination compounds and nomenclature Definition of coordination compounds Narrow sense: Coordination compounds are formed by ligand and central atom according to certain composition and space configurations. Broad sense: The compound forming by atom A and atom B or radical C, different from the original components, could be considered as coordination ones. Section 1 The basis of coordination chemistry 1.2 Definition of coordination compounds and nomenclature Nomenclature of coordination compounds The nomenclature of coordination compounds at present in china is IUPAC nomenclature system, developed and adopted by International Union of Pure and Applied Chemistry (IUPAC), adapted by China Chemistry Society. Section 1 The basis of coordination chemistry 1.3 Basic types of ligand and coordination ability Monodentate , H2O, NH3, PR3 ligand Multidentate , en, edta Macrocyclic , crown ether, porphyrin, Section 1 The basis of coordination chemistry 1.3 The basic types of ligand and coordination ability bidentate ligand Ethylene diamine 2,2- bipyridine 1,10-phenanthroline β-diketone Section 1 The basis of coordination chemistry 1.3 The basic types of ligand and coordination ability tridentate ligand Diethylene triamine Section 1 The basis of coordination chemistry 1.3 The basic types of ligand and coordination ability tetradentate ligand N,N‘-Bis(salicylidene) ethylenediamine cobalt salt Section 1 The basis of coordination chemistry 1.3 Basic types of ligand and coordination ability hexadentate ligand EDTA Section 1 The basis of coordination chemistry 1.3 Basic types of ligand and coordination ability macrocyclic ligand - crown ether 18-crown-6 complexes 15-crown-5 complexes Section 1 The basis of coordination chemistry 1.3 The basic types of ligand and coordination ability macrocyclic ligand - cryptand Cryptand[2,2,2] Section 1 The basis of coordination chemistry 1.3 Basic types of ligand and coordination ability coordination ability From monodentate ligand to chelating ligand, macrocyclic ligand, as the number of closed loop increases, their chemical binding to central metal atoms was strengthened. Section 1 The basis of coordination chemistry 1.4 Classification of the coordination compounds Based on number of central atom mononuclear and polynuclear coordination compound Based on type of ligand single ligand and mixed ligand coordination compound Based on number of ligand simple coordination compound, chelation, macrocyclic etc Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds 2.2 Isomerism of coordination compounds Section 2 Coordination stereochemistry 2.1 The geometry configuration of coordination compounds The geometry configuration of coordination compounds is closely related to the coordination number. The coordination number of metal complex is between 2 to 8. Rare earth metals has higher coordination number due to its larger ionic radius, usually between 8 to 12, but 3d transition metal mostly is 4 or 6. Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N = 2 Central metals are mainly Cu(I), Ag(I), Au(I), and Hg(II) (d10). Linear molecular geometry. Typical example: Cu(NH3)2+, AgCl2, Au(CN)2-, and HgCl2. Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N.= 3 Central metals are mainly Cu(Ⅰ), Hg(Ⅱ), Pt(0). Planar trigonal molecular geometry. Typical examples: HgI3-, D3h point group. Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N.= 4 (important configuration) square planar (D4h) tetrahedron (Td) Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N.= 5 trigonal bipyramid [CuCl5]3- [CuBr5]3- Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds Configuration changes trigonal bipyramid to tetragonal pyramid Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N.= 6 regular octahedron (Oh) tetragonal bipyramid (D4h) regular octahedron Distortion trigonal antiprism (D3d) Section 2 Coordination stereochemistry 2.1 The geometry configuration of coordination compounds tetragonal bipyramid (D4h) distorted along C4 axis regular octahedron (Oh) tetragonal bipyramid (D4h) Section 2 Coordination stereochemistry 2.1 The geometry configuration of coordination compounds trigonal antiprism (D3d) distorted along C3 regular octahedron (Oh) trigonal antiprism (D3d) Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N.= 7 single-capped octahedron (C3v) pentagonal bipyramid (D5h) single-capped triprism (C2v) Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N.= 8 For complexes with c.n. > 8, central metal ion usually need to satisfy the following conditions: (1) larger radius; (2) higher oxidation state; (3) less d-electron. Examples: Lanthanide, Actinide ions ( Ce(IV), U(VI) ) Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N.= 8 D4d D2d Oh C2v D6h Section 2 Coordination stereochemistry 2.1 The geometry configuration of coordination compounds C.N.= 9 Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N.=10 Dodecahedron (D2) Section 2 Coordination stereochemistry 2.1 Geometry configuration of coordination compounds C.N. = 12 Icosahedron (Ih) Section 2 Coordination stereochemistry 2.2 Isomerism of coordination compounds Definition of isomer Isomers are defined as compounds having the identical formula but different structures Section 2 Coordination stereochemistry 2.2 Isomerism of coordination compounds Classification of isomers ionization isomerism hydration isomerism constitutional isomerism linkage isomerism coordination isomerism isomers ligand isomerism stereoisomerism geometric isomerism optical isomerism Section 2 Coordination stereochemistry 2.2 The Isomerism of coordination compounds 2.2.1 ionization isomerism The distribution of ligand is different between external and internal. [Co(NH3)5Br]SO4 [Co(NH3)5(SO4)]Br (violet) (red) Section 2 Coordination stereochemistry 2.2 Isomerism of coordination compounds 2.2.2 hydration isomerism [Cr(H2O)6]Cl3 (violet) [Cr(H2O)5Cl]Cl2•H2O (green) [Cr(H2O)4Cl2]Cl•2H2O (green) Section 2 Coordination stereochemistry 2.2 Isomerism of coordination compounds 2.2.3 linkage isomerism ambident ligand NO2- yellow red Section 2 Coordination stereochemistry 2.2 Isomerism of coordination compounds 2.2.4 coordination isomerism The distribution of ligand is different between complex anion and cation. [Co(NH3)6][Cr(OX)3] and [Cr(NH3)6][Co(OX)3] [Cr(NH3)6][Cr(SCN)6] and [Cr(NH3)4(SCN)2][Cr(NH3)2(SCN)4] Section 2 Coordination stereochemistry 2.2 Isomerism of coordination compounds 2.2.5 ligand isomerism 1,2 - diaminopropane methylene diamine Section 2 Coordination stereochemistry 2.2 Isomerism of coordination compounds 2.2.6 geometric isomerism (cis-trans isomerism) planar square coordination compounds Section 2 Coordination stereochemistry 2.2 The Isomerism of coordination compounds 2.2.6 geometric isomerism(cis-trans isomerism) Octahedron complexes M(a4b2) type: cis-, and trans-; M(a3b3) type: fac-, and mer-; Section 2 Coordination stereochemistry 2.2 The Isomerism of coordination compounds 2.2.6 geometric isomerism (cis-trans isomerism) Section 2 Coordination stereochemistry 2.2 The Isomerism of coordination compounds 2.2.6 geometric isomerism(cis-trans isomerism) octahedron comlexes:M(a2b2c2) type 3 trans- 1 trans- and 2 cis- 3 cis- Section 2 Coordination stereochemistry 2.2 Isomerism of coordination compounds 2.2.7 optical isomerism A molecule, if cannot overlap with its mirror image after symmetric operation, it is called the optical isomer, or chiral molecule. Such as, cis-Co(en)(NO2)22+ is chiral. Section 2 Coordination stereochemistry 2.2 The Isomerism of coordination compounds 2.2.7 optical isomerism ethylene diamine glycine Section 3 Coordination chemistry theory 3.1 Development of coordination chemistry theory 3.2 Crystal field theory 3.3 Ligand field theory Section 3 Coordination chemistry theory 3.1 Development of coordination chemistry theory In 1893, Swiss chemist Alfred Werner, 26 years old, published a famous paper. It gives the basic conception of modern coordination bond, coordination number and structure of coordination compounds. Werner coordination theory plays a major role on the development of coordination chemistry, and thus won the Nobel Prize in chemistry in 1913. Section 3 Coordination chemistry theory 3.1 The development of coordination chemistry theory In 1929, L.Pauling put forward valence bond theory of coordination compounds. In 1929, Bethe and Van-Vleck put forward crystal field theory of coordination compounds. Later ligand field theory and molecular orbital theory formed. Section 3 Coordination chemistry theory 3.2 Crystal field theory In 1929, Bethe put forward crystal field theory. Crystal field theory is a static theory, but adding ligand makes original quintuple degenerate d-orbitals losing degeneracy of central atom. d-orbitals Section 3 Coordination chemistry theory 3.2 Crystal field theory Basic point of crystal field theory: (1) electrostatic interaction between M and L; (2) degenerated d-orbit split in crystal field; (3) d electron rearrangement within the splitted d orbits; Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting (1) spherical symmetry field Due to the negative charge of ligands distributed spherically, no matter where d-orbit is, the repulsive interaction of the negative charge is the same, although of the d-orbital energy increases, still keep quintet degenerate d-orbitals. Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting (2) regular octahedron field In regular octahedron field, the repulsive interaction of 5 d-orbitals will no longer be the identical. Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting (2) regular octahedron field free ion spherical symmetry field regular octahedron field Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting (2) regular octahedron field Energy level splitting conforms to the center of gravity conservation principle. 2E(eg)+3E(t2g)=0 E(eg)-E(t2g)=△o E(eg)=0.6△o = 6Dq E(t2g)=-0.4△o =-4Dq △o/10Dq is eg and t2g orbit energy difference Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting (3) elongated regular octahedron field In elongated regular octahedron field, eg and t2g orbit will split further. Energy order (from high to low): ① dx2-y2,②dz2,③dxy,④dxz and dyz Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting (4) square planar field In square planar field, eg and t2g orbit also will occur to split further. Energy order (from high to low): ① dx2-y2,②dxy,③dz2,④dxz and dyz Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting (5) regular tetrahedron field free ion spherical symmetry field regular tetrahedron field Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting (5) regular tetrahedron field According to the center of gravity conservation principle: △t=E(t2)-E(e)=(4/9)△o 3E(t2)+2 E(e)=0 Calculated: E(t2)=1.78Dq E(e)=-2.67Dq Section 3 Coordination chemistry theory 3.2 Crystal field theory d-orbit energy level splitting Section 3 Coordination chemistry theory 3.2 Crystal field theory Splitting energy and its influence factors: (1) the type of ligand field such as: △t = (4/9)△o (2) the oxidation state and radius of center ion Ion Co(H2O)62+ Δo(cm-1) 9300 Co(H2O)63+ 18600 Co(NH3)62+ 10100 the higher oxidation state,the larger Δ Co(NH3)63+ 23000 Section 3 Coordination chemistry theory 3.2 Crystal field theory Splitting energy and its influence factors: (3) the types of ligands Such as: ion Δo(cm-1) Cu(H2O)62+ 12600 Cu(NH3)42+ 15100 Cu(en)32+ 16400 for the same metal ion,Δo is different with different ligands Section 3 Coordination chemistry theory 3.2 Crystal field theory Splitting energy and its influence factors: (3) the types of ligands spectrochemistry order: splitting energy of common ligand arrange from small to large. (weak field) I- < Br- < S2- < Cl- < SCN- < NO3- < F- < OH- < H2O< NCS- < NH3 < en < bipy < phen < NO2- < CN- < CO (strong field) Section 3 Coordination chemistry theory 3.2 Crystal field theory Low-spin predictions of complexes High spin arrangement Weak Field Low spin arrangement Strong field Obviously, only one arrangement in d1, d2, d3, d8, d9, d10 , no difference between high and low spin. Section 3 Coordination chemistry theory 3.2 Crystal field theory Limitations of crystal field theory Crystal field theory can be better to illustrate the main issues of stereochemistry complexes and thermodynamic properties, but it can not reasonably explain the spectrochemistry order of ligands. This is due to the crystal field theory without considering the overlap of metal ions and ligands tracks, that does not recognize the existence of the covalent bond. Modern experimental determination indicate that the track rails of the ligands and the metal ions are indeed overlap. Section 3 Coordination chemistry theory 3.3 Ligand field theory Solution of crystal field theory limitations covalent bonds molecular orbital theory Propose crystal field calculation method Base on Crystal field theory Ligand field theory. Section 3 Coordination chemistry theory 3.3 Ligand field theory Key points of complex ligand field theory (1) the ligand is not a point charge without details, but there is a certain charge distribution. (2) The binding contain both the electrostatic and covalent interactions. Section 4 Reaction mechanism of complex 4.1 Active and inertia of coordination compounds 4.2 The mechanism for substitution reactions 4.3 Factors of influencing the substitution reaction rate Section 4 Reaction mechanism of complex 4.1 The active and inertia of coordination compounds Active coordination compounds: fast ligand exchange in substitution reaction; Inertia coordination compounds: slow ligand exchange in substitution reaction. Coordination compounds activity base on the kinetics, but coordination compounds stability base on the thermodynamics. Section 4 Reaction mechanism of complex 4.1 The active and inertia of coordination compounds activator activation energy activity reaction energy stability reactant product Section 4 Reaction mechanism of complex 4.2 The mechanism for substitution reactions Substitution reactions mechanism: nucleophilic substitution(SN): MLn + Y → MLn-1Y + L electrophilic substitution(SE): MLn + M’ → M’Ln + M nucleophilic substitution: SN1 and SN2 mechanism Section 4 Reaction mechanism of complex 4.2 The mechanism for substitution reactions 1 SN1 reaction mechanism(mono-molecule substitution reactions) two steps: (1) ML6 → ML5 + L (slow) (C.N. = 5) (2) ML5 + Y → ML5Y (fast) The first step is to determine the rate of reaction, and the total rate depends on [ML6]. Such as: (1) M(H2O)62+ → M(H2O)52+ + H2O (slow) ( M = Cu……) (2) M(H2O)52+ + H2O* → [M(H2O)5(H2O*)]2+ (fast) Section 4 Reaction mechanism of complex 4.2 The mechanism for substitution reactions 2. SN2 reaction mechanism(bimolecular substitution reactions) two steps: (1) MLn + Y → MLnY (slow) (C.N. = 7) (2) MLnY → MLn-1Y + L (fast) The total rate depends on [MLn] and [Y]. Such as: [Pt(NH3)3Cl]+ + Br- → [Pt(NH3)3Br]+ + Clrate equation: v = k[Pt(NH3)3Cl+][Br-] 2nd-order reaction Section 4 Reaction mechanism of complex 4.3 Factors of influencing the substitution reaction rate key factor: Static electricity theory Internal and external orbital theory(Taube rule) Crystal field theory Section 4 Reaction mechanism of complex 4.3 Factors of influencing the substitution reaction rate 4.3.1 Static electricity theory key factor: the Z and r of M, L, Y SN1: larger r of L, M-L bond easily breaking, be beneficial to SN1 such as: [Co(NH3)5Br]2+ + H2O = [Co(NH3)5(H2O)]3 ++ Br[Co(NH3)5Cl]2+ + H2O = [Co(NH3)5(H2O)]2 ++ Cl- (fast) (slow) lower Z of M, M-L bond easily breaking, be beneficial to SN1, such as: [Fe(H2O)6]2 ++ H2O* = [Fe(H2O)5(H2O*)]2+ + H2O (fast) [Fe(H2O)6]3 ++ H2O* = [Fe(H2O)5(H2O*)]3+ + H2O (slow) Section 4 Reaction mechanism of complex 4.3 Factors of influencing the substitution reaction rate 4.3.1 Static electricity theory SN2: smaller r, higher Z of L, and higher Z of M, be beneficial to SN2 [Co(NH3)5(H2O)]2+ + I- = [Co(NH3)5I]+ + H2O [Co(NH3)5(H2O)]2++ Cl- = [Co(NH3)5Cl]+ + H2O (slow) (fast) Section 4 Reaction mechanism of complex 4.3 Factors of influencing the substitution reaction rate 4.3.2 Internal and external orbital theory(Taube rule) activity Inertia Section 4 Reaction mechanism of complex 4.3 Factors of influencing the substitution reaction rate 4.3.3 Crystal field theory CFAE = CFSE(Oh) - CFSE(int) CFAE- Crystal field activation energy; CFSE(Oh)- Crystal field stabilization energy; CFSE(int) – intermediate crystal field stabilization energy great CFAE represent inertia complex, otherwise activation complex 5.New functional coordination compounds As development of advanced technology , research about functional complexes (molecular-based magnetic materials) with special optical , electric , thermal , magnetic character was developed rapidly . Conductive complexes Magnetic complexes Nonlinear optical complexes Photoluminescence complexes Electroluminescent complexes Medical complexes 5.New functional coordination compounds The research of molecule-based materials is a new and hot science between chemistry, physics, biology. Molecule-based materials is defined as useful substances with molecules compose combined with molecules or changed molecules. As the different optical, magnetic, electrical characters of molecule-based materials , we can call them as optical molecularbased material, molecular conductor and molecular magnetic materials. 5.New functional coordination compounds 5.1 Conductive Complexes 5.2 Magnetic Complexes 5.3 photoluminescence/electroluminescence complexes 5.4 Medical Complexes 5.5 Coordination Polymers 5.New functional coordination compounds 5.1 Conductive complexes Conductive complexes ( molecular conductor ) have their own superiority 1) small density (1.5~2.0 g·cm-3,vs. copper: 8.9g·cm-3 ); 2) easy to adjust and reform; 3) Suitable for molecular electronics. 5.New functional coordination compounds 5.1 Conductive complexes Conductive complexes can divide into two broad categories: Low dimensional coordination polymers: phenolphthalein porphyrin Charge transfer complexs: Fullerene , metal salt ,we can also call them electron donors–receptor ligand compound 5.New functional coordination compounds 5.1 Conductive complexes Low dimensional coordination polymers: It can show the characteristics of the molecular conductor when the aggregation state of conjugate surface complexes are stratified structure . According to the type of interactions between the molecules of this kind of conductive polymer ligand, we can divided into: M - M, M – p, and p - p three categories. 5.New functional coordination compounds 5.1 Conductive complexes M-M type low dimensional coordination polymers : K2[Pt(CN)4]Br0.3·3H2O is relied on the extending of the dz2 orbital overlap of neighboring central metal ion (M - M type, the distance between metal ion usually less than 0.3 nm) , it can form onedimensional metal conductive channel which electrons can transmission between column. 5.New functional coordination compounds 5.1 Conductive complexes This kind of one-dimensional molecular crystal metal properties satisfy the two conditions: Part of its structural units (molecular) HOMO orbit was occupied. Crystal molecular arrangement is beneficial to the frontier orbital overlap between moleculars. The 1D conductor has the following characteristics: Strong anisotropy 5.New functional coordination compounds 5.1 Conductive complexes Low dimensional coordination polymers (M-M type) Phthalocyanine (pc) is a kind of macrocyclic plane conjugated ligands with 18 p electronic system (N4 ligand). Phthalocyanine complexes doped iodine after partial oxidation, their energy gap decreases, conduction band and valence band width, the conductivity significantly increased. For Pt, Fe, Ru and Mn coordination polymers, their conductive (M - M type) form was obtained by the metal atoms dz2 orbital overlap .The carrier is electron. 5.New functional coordination compounds 5.1 Conductive complexes Low dimensional coordination polymers (π -π type) For Cu, Ni and other coordination polymer,the p-orbit overlapping of the phthalocyanine ligand molecular form the one dimensional conductive column which plays a role of electronic transferring (hole). In this type of metal complexes, the electrical conductivity is only influenced by π -π overlapping of macrocyclic ligands and has nothing to do with the metal center. 5.New functional coordination compounds 5.1 Conductive complexes Low dimensional coordination polymers (M -π type) In one-dimensional polymer phthalocyanine metal complexes use conjugate molecules as bridging ligand , when the metal dxz and dyz orbital overlap track and large ring dentate orbital, forbidden band width become smaller and the M -π type can show the electrical conductivity. [PcMCN] ∝(M = Cr, Mn , Fe, Co and Rh etc) show the conductivity of 10-4~10-2S·cm-1 without dopping 5.New functional coordination compounds 5.1 Conductive complexes Charge transfer complexes: The molecular metallic charge transfer salt formed by the electron donor D and electron acceptor A can be divided into three categories, DA, DX and CA type (C represent for cation, X represent for anion). But the conductive mainly comes from part D and A. 5.New functional coordination compounds 5.1 Conductive complexes From the electronic and spatial structure theory, many electron donors and acceptors was designed and sythesized. 5.New functional coordination compounds 5.1 Conductive complexes Electron accepter 5.New functional coordination compounds 5.1 Conductive complexes The charge transfer complexes is also called the electron donoracceptor ligand compounds: The first organic metal was obtained by combination with donor– acceptor (TTF:TCNQ 1:1) with metal electrical conductivity. (DA type) In 1980, The first atmospheric molecular superconductors (TMTST)2ClO4 was prepared by tetramethyl four selenium fulvalence .(DX type) 5.New functional coordination compounds 5.1 Conductive complexes DA Conductor As the first organic metal TTF-TCNQ, the concept of nature organic matter and complexes was changed. In this compound, charge transfer occurred between the electron donors TTF (D) and the receptor TCNQ (A) . 5.New functional coordination compounds 5.1 Conductive complexes DX Conductor Typical representative of the first generation of organic superconductor compounds (TMTSF)2X (X represent for anion, such as PF6-, AsF6-, ClO4-, etc), can turn to superconductors with pressure. 5.New functional coordination compounds 5.1 Conductive complexes Outlook Various types of excellent conductors, even the low temperature superconductors through the research on conductive complexes have been obtained. They are small crystals with poor mechanical strength, unlike traditional metal superconductors which can be processed. It is possible to make semiconductor molecules into the superconductor by modifying the structure of complexes and was potentially available as the molecular electronic devices in the future. That’s why physicists, materials scientists and biologists pay attention to it. 5.New functional coordination compounds 5.2 Magnetic complexes Magnetic complexes easily soluble in organic solvent which make it possible to obtain special magnetic material by ordinary chemical reaction in normal conditions. And molecular ferromagnet has advantages of small volume, light weight, various structures and easy to processing molding, can be used for aerospace materials, microwave absorption stealth materials, electromagnetic shielding materials and information storage materials, etc. It is a hot research field of coordination chemistry to synthesis molecular ferromagnet complexes with high phase transition temperature (Tc, known as the critical temperature). 5.New functional coordination compounds 5.2 Magnetic complexes Currently, magnetic complexes is the most widely researched of the molecular magnets, it can be formed mononuclear and binuclear and polynuclear complexes. It can form a onedimensional, two-dimensional and three-dimensional molecular magnets by proper molecular assembly of high spin complexes. 5.New functional coordination compounds 5.2 Magnetic complexes molecule ferromagnet: [{NiII(tn)2}5{FeIII(CN)6}3]n(ClO4)n·2.5nH2O reaction : 1,3-propylene amine, Ni(ClO4)2·6H2O, K3[Fe(CN)6]. 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes When illuminate some substances, these substances will emit visible light with various wavelength and intensity, When the illuminattion stop, the light emission also disappear, which is called photoluminescence (PL). And the electroluminescent(EL) is about the material can be sparked by the corresponding electricity to produce luminescence phenomenon under a certain electric field. 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes The photoluminescence and electroluminescence have common research point what is having a high luminous efficiency. Due to the special molecular structure of the metal complexes , on the one hand, its molecular structure rigidity, on the other hand, its molecular stability. 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes Light-emitting principle: ligand center light-emitting Metal complexes as a molecular whole, light absorbed by the ligand of photosensitive functional groups, and luminescence was originated from the electron transition between the orbitals on the ligands. 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes Metal ions, the equivalent of a inert atoms, combine with different parts of the organic ligands form chelate ring. And the original nonrigid flat structure change into a rigid plane one, which resulted in organic compounds without fluorescence into a strong fluorescence complexes. For example, non-fluorescence 8hydroxyquinoline have the green fluoresence in the chelate of tris (8hydroxyquinoline) aluminium (AlQ3) . 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes Light-emitting principle: the light-emitting on center ion If the m* level is below the T1 level in the complexes , it will happen the intramolecular energy transfer as : S1 T1 m*. This complexes of metal ions sensitized by organic match physical quantity transfer, its fluorescence intensity is much stronger than pure inorganic metallic ion. 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes Rare earth complexes with high luminescence efficiency and high color purity, covering the visible area. Advantages: narrow half-peak width; modify the structure of the ligand does not affect the luminescence spectra of center ion Applications: agricultural luminescent material, anti-counterfeiting materials, fluorescent and color display, electroluminescent 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes (1) Application in agriculture Rare earth complexes luminescence materials can effectively transform the sun‘s ultraviolet light into a red orange light which benefit for crop growth. The fluorescent conversion agricultural film (turn light film) based on the rare earth complexes can be used for vegetables, seedings, flowers, etc. 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes (2) Primary fluorescence and the application in color display Polymer complexes containing rare earth Ln3+, Tb3+ and Eu2+ can produce red, green and blue color fluorescence under uv excitation ,they can be made in three primary colors of composite polymer materials, plastic type tricolor fluorescent lights or color display 5.New functional coordination compounds 5.3 Photoluminescence/Electroluminescent complexes (3) Medical application of the rare earth complexes as fluorescent markers Fluorescent tags -- fluorescence immunity analysis. Long fluorescent life of the rare earth complexes Sharp band High sensitivity in extremely dilute concentrations serum protein the application prospect is very optimistic. 5.New functional coordination compounds 5.4 Medical Complexes Platinum Antitumor Drugs Complexes of platinum are the most widely used anticancer drugs, there are four complexes in clinical use, in addition to, a dozen complexes are on different stages of clinical trials, including an oral administration tetravalent platinum compound. (1) cisplatin 1965 discovered by American physiologist B. Rosenberg; 1978 approved for clinical use in the United States - the first inorganic anti-cancer substances 1997 comprehensive evaluation of anti-cancer drugs by World Health Organization Cisplatin ranked second (Adriamycin ranked first) Combination with cisplatin anti-cancer drugs - control or delay vomiting ondansetron, paclitaxel 5.4 Medical Complexes (1).Cisplatin First generation Advantages: Strong anti-cancer effect, high anti-cancer activity, conducive to clinical drug combination Disadvantages: Cause strong nausea and vomiting, toxic side effects, nephrotoxicity Anticancer application of cisplatin : ovarian cancer, lung cancer, cervical cancer, nasopharyngeal cancer, head and neck squamous cell carcinoma, prostate cancer, bladder cancer, testicular cancer, lymphosarcoma. 5.4 Medical Complexes (2).Carboplatin Second generation • In the 1980s, U.S. Bristol Myers Squibb, Cancer Research UK, and Johnson Matthey company jointly develop the carboplatin; • In 1990 carboplatin was successful developed in our country and approved listing. 5.4 Medical Complexes (2).Carboplatin • Good chemical stability - effectively reduce the vomiting • Good water solubility, 16 times of cisplatin - effectively reduce the nephrotoxicity • Myelosuppression, large blood toxicity If cisplatin is prescriptible for the cancer , carboplatin is also prescriptible, and the side effects (non-blood system) and induced vomiting of carboplatin is less than cisplatin, so people inclined to use carboplatin in current clinical. 5.4 Medical Complexes (3).Nedaplatin Second generation • Features: No renal toxicity after hydration and diuresis; Bone marrow suppression (Similar with carboplatin) Pharmacodynamic application of Nedaplatin : • leukemia, lung cancer, melanoma -- Anti-tumor effects better than cisplatin • head and neck cancer, testicular cancer, esophageal cancer, bladder cancer, ovarian cancer, cervical cancer-- Promised rate ≧ 25% • If cisplatin is prescriptible for the cancer , Nedaplatin is also prescriptible, and the effect of Nedaplatin is similar to or even better than cisplatin 5.4 Medical Complexes (4).Oxaliplatin Third generation •Be curative for leukemia (cisplatin resistance, that is non-active efficacy) •Good effect activity for the advanced colorectal cancer (colon cancer) • Good effect for a variety of tumors-- colorectal cancer, breast cancer, ovarian cancer -- and even has inhibitory effect for the first and second generation platinum-based anticancer drug-resistant strains 5.4 Medical Complexes (5).Lobaplatin Third generation Equal or better efficacy than the first-generation and second-generation; Considerable toxicity with carboplatin and no crossresistance with cisplatin; Good effect on the esophageal cancer. 5.4 Medical Complexes (6). Other third-generation platinum-based anticancer drugs • Ring Platinum -- Less toxic than cisplatin (thrombocytopenia), high activity than carboplatin; poor specificity, easy to damage normal cells • BBR3464-- Triple platinum complexes, multi-bonded with DNA, strong damage to DNA , high anti-tumor activity • ZD0473-- High activity of the tumor cells for secondgeneration drug resistance, orally active 5.4 Medical Complexes Gadolinium complex and magnetic resonance imaging (MRI) MRI technology has become one of the most powerful clinical diagnostic testing means. Diagnosis of the disease: using the foreign paramagnetic agents or imaging agent to make 1H(mainly water) in the normal and diseased tissues to produce a difference in resonance signals. Magnetic resonance contrast agents make proton relaxation time shortened, thus it improve tissue imaging results. Most magnetic resonance imaging agents are Gd (III), Mn (II) and Fe (III) complexes etc. . 5.5 Coordination Polymers Coordination Polymers The concept of coordination polymers. was first proposed in J. Am. Chem. Soc. by R.Robson in 1989 . The first coordination polymer synthesized by Robson is a threedimensional polymer built by the monovalent copper ions with the organic ligand 4,4 ', 4 ", 4"' - 4-cyano-phenyl-methane . Similar to the three-dimensional network structure of diamond configuration. 5.5 Coordination Polymers Coordination Polymers Maintain the characteristics of both the organic polymer and inorganic metal ; Polymer materials with new structure and peculiar properties; It may become functional materials with thermal, electrical, magnetic, catalytic and biological effects; One of the most attractive research direction in inorganic chemistry, materials chemistry , life sciences and other fields .