Exploration of 1‐Arylmethyl‐1, 3‐diphosphacyclobutane‐2, 4‐diyls as Hole Transfer Materials. Issue 12 (11th August 2016)

• Record Type: Journal Article
• Authors: Ito, Shigekazu; Torihata, Yushi; Mikami, Koichi
• Is Part Of: ChemistrySelect. Volume 1:Issue 12(2016)
• Page Start: 3310
• Page End: 3315
• Publication Date: 2016-08-11
• Subjects: Charge transfer -- Crystal engineering -- Density functional calculations -- Phosphorus heterocycles -- Semiconductors; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201600888
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: This paper describes the p‐type semiconductor characteristics of 1‐arylmethyl‐substituted air‐tolerant 1, 3‐diphosphacyclobutane‐2, 4‐diyls, focusing preliminarily on their hole transfer parameters deduced from their crystal and density functional theory (DFT) structures. 1‐(2‐Anthrylmethy)‐3‐ t ‐butyl‐2, 4‐bis(2, 4, 6‐tri‐ t ‐butylphenyl)‐1, 3‐diphosphacyclobutane‐2, 4‐diyl functions as a p‐type field‐effect transistor (FET) with semiconductor parameters comparable to its benzyl‐substituted derivative. Thienylmethyl groups induced the FET response, and thus we investigated the utility of the 2‐thieno[3, 2‐ b ]thiophenemethyl group. Critical parameters, including reorganization energies ( λ ), hole couplings ( V ), and hole hopping rates ( W ) were estimated based on experimental and DFT data. The benzyl and 2‐anthrylmethy groups constructed hole transfer pathways comparable to that of acenes, whereas the 2‐thieno[3, 2‐ b ]thiophenemethyl substituent resulted in the assembly of a unique three‐dimensional network. The findings described in this study may lead to the fabrication of superior FET devices based on the chemistry of 1, 3‐diphosphacyclobutane‐2, 4‐diyl. Abstract : The extremely air‐stable crystalline benzyl‐, 2‐anthrylmethyl‐, and thieno[3, 2‐ b ]thiophenemethyl‐substituted 1, 3‐diphosphacyclobutane‐2, 4‐diyls functioned as p‐type FET devices. The hole hopping characteristics are discussed based on the experimentally determined packing motifs.