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Highly Oxidized Semiconducting Coordination Polymers – Coupled Oxidation and Coordination of Guanidine Electron Donors
Author(s) -
Trumm Christine,
Stang Simone,
Eberle Benjamin,
Kaifer Elisabeth,
Wagner Norbert,
Beck Johannes,
Bredow Thomas,
Meyerbröker Nikolaus,
Zharnikov Michael,
Hübner Olaf,
Himmel HansJörg
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201101325
Subject(s) - chemistry , dication , guanidine , benzene , polymer , inorganic chemistry , coordination polymer , coordination complex , ion , band gap , thermal stability , redox , salt (chemistry) , conductivity , crystallography , polymer chemistry , metal , organic chemistry , physics , quantum mechanics
Redox and coordination processes are coupled in the course of reactions of the organic electron donors 1,2,4,5‐tetrakis(tetramethylguanidino)benzene ( 1 ) and 1,2,4,5‐tetrakis( N , N′ ‐dimethyl‐ N , N′ ‐ethyleneguanidino)benzene ( 2 ) with silver salts. Experiments with several different silver salts show that the product structure is significantly affected by the properties of the anion in these salts. Chain polymers are the products of reactions with AgPF 6 or AgBF 4 , in which dicationic organic building blocks are connected by silver ions. Experiments with AgNO 3 yielded either dinuclear complexes (with 1 ) or 2D networks (with 2 ). If the salt Ag[Al{OC(CF 3 ) 3 } 4 ], featuring a weakly coordinating anion, was used, simple silver‐free salts of the guanidine dication were obtained. The thermal stability, optical properties, and electrical conductivity were studied in detail for the product polymer {[( 1 )Ag](PF 6 ) 3 } n . From the temperature dependence of the electric conductivity, this compound was found to be a semiconductor with a band gap of approximately 3 eV. The experiments were complemented by quantum chemical calculations at density‐functional‐theory level on the band structure of this and a related polymer. The electronic situation was further analyzed with the aid of molecular model complexes, which were either synthesized or calculated.