Abstract

A series of new copper(II)-azido complexes of 1D polymeric chains of [Cu(L1)(μ1,3-N3)]n (1) and [Cu(L2)(μ1,3-N3)]n (2), and binuclear [Cu(L3)(μ1,1-N3)]2 (3) [HL1 = N-butyl-N-(5-bromosalcylidine)ethane-1,2-diamine, HL2 = N-butyl-N-(5-chlorosalcylidine)ethane-1,2-diamine, HL3 = N-butyl-N-(salcylidine)ethane-1,2-diamine] have been synthesized and characterized. Characterizations of 1–3 have been accomplished by usual physico-chemical techniques such as elemental analysis, FTIR, UV–vis and single crystal X-ray diffraction studies. X-ray diffraction analyses of 1 and 2 reveal that the monomeric units of 1D polymers are interconnected via the μ1,3-azido bridging. The coordination geometry around the copper(II) centers in 1 and 2 can be best described as distorted square pyramidal environments. Complex 3 shows a centrosymmetric structure with two copper(II) centers that are held together by μ1,1-azido bridging in a distorted square pyramidal environment. In the electrical studies of 1–3, both direct current (dc) and alternating current (ac) analyses have been carried out based on the metal-complex (1/2/3)-metal (M-S-M) structures. The sheet resistance of the deposited films and the metal-complex contact resistance are estimated by employing transfer length method (TLM) measurements. The dark current-voltage characteristics of Al-complex (1/2/3)-Al structures are analyzed by considering dual back-to-back Schottky barrier diode structure. The voltage variations of the device current under illumination (400–700 nm) clearly demonstrate the photo-sensitivity of these materials. The catalytic activities of 1–3 have been investigated towards aerial oxidation of 3,5-di-tert-butylcatechol. All three complexes exhibit potential catalytic effectiveness towards oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butyl-o-quinone (3,5-DTBQ) with turnover numbers 14.76, 33.92 and 81.02 h−1 for 1, 2 and 3, respectively.

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