T‐Shaped (Donor–π–)2Acceptor–π–Donor Push–Pull Systems Based on Indan‐1, 3‐dione. Issue 24 (20th July 2015)

• Record Type: Journal Article
• Authors: Solanke, Parmeshwar; Bureš, Filip; Pytela, Oldřich; Klikar, Milan; Mikysek, Tomáš; Mager, Loic; Barsella, Alberto; Růžičková, Zdeňka
• Is Part Of: European journal of organic chemistry. Issue 24(2015)
• Page Start: 5339
• Page End: 5349
• Publication Date: 2015-07-20
• Subjects: Donor–acceptor systems -- Chromophores -- Electrochemistry -- Nonlinear optics -- Density functional calculations; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201500525
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: Sixteen model (donor–π–)2 acceptor–π–donor [(D–π–)2 A–π–D] molecules with an extraordinary T‐shaped arrangement were designed and synthesized. Indan‐1, 3‐dione was employed as a central acceptor with electron donors linked at the C‐2, C‐4, and C‐7 positions. These push–pull molecules represent a first systematic modification of an indan‐1, 3‐dione‐fused benzene ring. The structures and properties of all target molecules were investigated by X‐ray analysis, electrochemistry, UV/Vis absorption spectroscopy, differential scanning calorimetry, electric‐field‐induced second‐harmonic generation (EFISHG) studies, and DFT calculations. A thorough evaluation of all of the gathered data has been performed, and structure–property relationships were evaluated. Electron donors attached at the C‐2 position through π systems of various lengths affect the studied properties most significantly. The side donors at C‐4 and C‐7 can be described as auxiliary and do not dominate the observed properties. However, thiophene is a more efficient donor than N, N ‐dimethylaniline in this respect. Hence, indan‐1, 3‐dione bearing a piperidylthiophene donor connected through a propenylidene spacer at C‐2 completed with two side thiophen‐2‐ylethynyl branches at C‐4 and C‐7 showed the highest figure of merit among the studied properties. Abstract : T‐shaped chromophores based on an indan‐1, 3‐dione central acceptor with systematically varied peripheral donors are investigated by X‐ray analysis, electrochemistry, UV/Vis absorption spectroscopy, differential scanning calorimetry (DSC), electric‐field‐induced second‐harmonic generation (EFISHG) studies, and DFT calculations. Structure–property relationships are subsequently elucidated.