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Synthesis, Structures and Properties of CuⅠ,Ⅱ and CdⅡ Coordination Polymers of Tetrazole Ligands

Author: LiXiangNan
Tutor: YinYeGao
School: Shantou University
Course: Inorganic Chemistry
Keywords: Tetrazole Nanotube Coordination Polymer Crystal Structure luminescence
CLC: O634
Type: Master's thesis
Year: 2011
Downloads: 253
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Abstract


Coordination polymers （CPs） of polyazoles are a kind of compounds especially interesting to structural chemistry and material science. Due to the flexible coordination habit of polyazole ligands, CPs based on such ligands show show great interest in ligand-dominated architecture and the structure-based functions.In order to probe the effect of reaction conditions on the dentation of polyazole ligands and further the assembly of Cu（I, II） and Cd（II）-azolate CPs and so to elicit conclusions applicable for design of CPs and beneficial to the study of structure-property correlation, we performed the reactions of 5-（3-pyridyl）tetrazole （3-Hptz） or 2,3-bis （tetrazo-5-yl）pyrazine （H2dtp） with copper and cadmium salts under different conditions and consequently obtained 14 CPs. The CPs have been structurally defined and photophysically investigated, through which we had an awareness of the impact of non-constitutional factors, such as temperature, stoichiometry, solvent and so on, on the construction and functionalities of CPs. Herein we summarize the lab outcomes into a dissertation as six chapters.Chapter 1 briefly reviews the history and on-going progress of coordination chemistry, and meanwhile cites the factors influencing construction of CPs. Next, it highlights the importance of iodocuprate clusters as building blocks and functional carriers for fabricating photoemissive CPs, exemplifies the chirality transfer from ligand to metal centers and how to design chirality metal–organic frameworks, and then simply introduces the application of tetrazoles as elements of topologically novel CPs, and finally, gives a justification for choosing tetrazolate CPs as topic.In Chapter 2, the thermal syntheses, solid structures and properties of five 3D coordination polymers, comparably based on the deprotonated 3-ptz and cationic iodocuprate entities, are described. The CPs are isolated under varied conditions and so they are diversely structured to confirm the influence of operation variables on assembly of CPs. Thereinto, 1 and 2 are actually isomeric, possessing a formula of [（Cu7I4）（ptz）3]n, of which 1 is a conglomerate consisting of equimolar enatiomers 1αand 1β, while 2 is a meso condensate made of paired enantiomeric ptz’s and （Cu7I4）3+ motifs. In a view of structural crystal engineering, the isolation of 1αand 1βas optical isomers embodies a rare spontaneous resolution of chiral bulks, and isolation of 1 and 2 as diastereomers exemplifies a novel stereochemistry of chiral building blocks in the process of self-assembly. 3-5 are comparable in 3D and, in contrast to 1 and 2, composed of anionic ptz’s and infinite cationic iodocuprate entities. For example, 3 shows a modular assembly of ptz’s and [（Cu7I4）3+]n chains, 4 exhibits an incorporation of ptz’s and 2D （Cu3I2+）n networks and 5 consists of ptz’s and 1D （Cu2I +）n chains.Chapter 3 includes two Cd（II） CPs, i. e. [Cd（ptz）2]n （6） and [Cd2（ptz）2Cl2]n （7）, which were resulted from reactions of 3-ptz with CdCl2 in two ratios. The separately categorized CPs are similarly assembled as 3D structures, but different without or with Cl- as building element and in emission. More interestingly the thermogravimetric plots of 6 and 7 reveals that the metal component of 6 at 800oC remains as element metal residue, but that of 7 is liberated likely in a volatile CdCl2 form, therewith demonstrating an effect of stoichiometry on constructions and properties of CPs.Chapter 4 describes the syntheses and structures of four copper CPs of H2dtp, namely [Cu8（dtp）4（H2O）3]n （8）, {[Cu2（dtp）2Cu（H2O）4]（H2O）2}n （9）, [Cu（dtp）（H2O）2]n （10） and {[Cu（dtp）]（CH3）2NH2}n （11）, of them, 8 and 9 were obtained at varied temperatures and thus their resulting as Cu（I） and Cu（I,II） CPs respectively indicates a thermodynamic favorability of 8 and a kinetic of 9. Harvest of 10 differs from that of 9 with adding isonicotine as additive. This led to the divalence of all copper ions. Preparing of 11 is in contrast to that of 9, using DMF in the place of NH3, and this led to the 2D CP with protonated dimethylamines that are produced from decomposition of DMF as counter ion. Besides, the thermogravimetric plot of 11 indicates a stability to heat up to 310oC and its emission spectrum suggests a qualification of a green luminophore.Chapter 5 describes the structures of [Cu2（dtp）2CN（H2O）2]n （12）,[Cu5（dtp）2CN（H2O）3]n （13） and [Cu6（dtp）2（CN）2（H2O）3]n （14）, the CPs prepared by the thermal reactions of H2dtp with CuCN. Of the caynocuprates, 12 is uniquely assembled in a 1D“zigzag”chain, where the CN groups play terminal ligands, but 13 and 14 are 3D net, defining a bridging function of CNs.Chapter 6 is a conclusion to the whole article.

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