Synthesis and applications of main-chain Ru(ii) metallo-polymers containing bis-terpyridyl ligands with various benzodiazole cores for solar cells

Abstract

A series of p-conjugated bis-terpyridyl ligands (M1-M3) bearing various benzodiazole cores and their corresponding main-chain Ru(II) metallo-polymers were designed and synthesized. The formation of metallo-polymers were confirmed by NMR, relative viscosity, and UV-visible titration measurements. The effects of electron donor and acceptor interactions on their thermal, optical, electrochemical, and photovoltaic properties were investigated. Due to the strong intramolecular charge transfer (ICT) interaction and metal to ligand charge transfer (MLCT) in Ru(II)-containing polymers, the absorption spectra covered a broad range of 260-750 nm with the optical band gaps of 1.77-1.63 eV. In addition, due to the broad sensitization areas of the metallo-polymers, their bulk heterojunction (BHJ) solar cell devices containing [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) as an electron acceptor exhibited a high short-circuit current (J sc ). An optimum PVC device based on the blended polymer P1 : PCBM ¼ 1 : 1 (w/w) achieved the maximum power conversion efficiency (PCE) value up to 0.45%, with V oc ¼ 0.61 V, J sc ¼ 2.18 mA cm À2 , and FF ¼ 34.1% (under AM 1.5 G 100 mW cm À2 ), which demonstrated a novel family of conjugated polyelectrolytes with the highest PCE value comparable with BHJ solar cells fabricated from ionic polythiophene and C 60 .

Optical properties of amphiphilic copolymer-based self-assemblies

“…The resulting polymers possess rich functions derived both from their metallic elements and polymer chains. The architectures of coordination polymers rely on the metal-ligand bonds which link the two segments [39,40]. Several representative coordination polymers with different architectures are shown in Fig.…”

Self‐Assembly of Conjugated Units Using Metal‐Terpyridine Coordination

“…As we understand it, this modest performance probably originates from the ambiguous polymer molecular weight and molecular weight distribution, unknown secondary or higher structural order of the polymer, and its as yet unclear photodynamics. Present methods for determination of molecular weight in metallopolymers include end‐group calculation from NMR integration data and viscosity experiments, which suffer respectively from the limited ratio of end moieties to inner moieties and inherent uncertainty of NMR experiments (ca. 5%) for the former, and lack of standard materials for the latter to provide accurate data.…”

Recent Developments in the Synthesis and Applications of 1,2,5-Thia- and Selenadiazoles. A Review

“…Treatment of 4,7-dibromo-2,1,3-benzoselenadiazole (198) with arylboronic acids 225,226 or their pinacol esters 111,227 in the presence of tetrakis(triphenylphosphine)palladium(0) [Pd(PPh 3 ) 4 ] and sodium or potassium carbonates gave 4,7-diaryl-2,1,3-benzoselenadiazoles 199 and 200 in high to moderate yields (Scheme 100).…”

“…107,108 Hexylthiophene-and substituted fluorene-boronic acid pinacol esters 116 were successfully used in the reaction with dibromobenzothiadiazole (112) producing the corresponding 4,7-bis(aryl)-2,1,3-benzothiadiazoles 114 in high yields (Scheme 54). [109][110][111][112][113] …”