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Directly Connected AzaBODIPY-BODIPY Dyad: Synthesis, Crystal Structure, and Ground- and Excited-State Interactions

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Title Directly Connected AzaBODIPY-BODIPY Dyad: Synthesis, Crystal Structure, and Ground- and Excited-State Interactions
 
Creator KUMAR, S
GOBEZE, HB
CHATTERJEE, T
D'SOUZA, F
RAVIKANTH, M
 
Subject PHOTOINDUCED ELECTRON-TRANSFER
REACTION CENTER MIMICRY
PHOTODYNAMIC THERAPY
ENERGY-TRANSFER
CHARGE SEPARATION
SOLAR-CELLS
AZA-BODIPY
LASER-DYES
BORON
FULLERENE
 
Description Directly connected, strongly interacting sensitizer donor-acceptor dyads mimic light-induced photochemical events of photosynthesis. Here, we devised a dyad composed of BF2-chelated dipyrromethene (BODIPY) directly linked to BF2-chelated tetraarylazadipyrromethene (azaBODIPY) through the beta-pyrrole position of azaBODIPY. Structural integrity of the dyad was arrived from two-dimensional NMR spectral studies, while single-crystal X-ray structure of the dyad provided the relative orientation of the two macrocycles to be similar to 62 degrees. Because of direct linking of the two entities, ultrafast energy transfer from the (BODIPY)-B-1* to azaBODIPY was witnessed. A good agreement between the theoretically estimated Forster energy transfer rate and experimentally determined rate was observed, and this rate was found to be higher than that reported for BODIPY-azaBODIPY analogues connected with spacer units. In agreement with the free-energy calculations, the product of energy transfer, (1)azaBODIPY* revealed additional photochemical events such as electron transfer leading to the creation of BODIPY center dot+-azaBODIPY(center dot-) radical ion pair, more so in polar benzonitrile than in nonpolar toluene, as evidenced by femtosecond transient spectroscopic studies. Additionally, the spectral, electrochemical, and photochemical studies of the precursor compound azaBODIPY-dipyrromethane also revealed occurrence of excited-state events. In this case, electron transfer from the (1)azaBODIPY* to dipyrromethane (DPM) yielded DPM center dot+-azaBODIPY(center dot-) charge-separated state. The study described here stresses the role of close association of the donor and acceptor entities to promote ultrafast photochemical events, applicable of building fast-response optoelectronic and energy-harvesting devices.
 
Publisher AMER CHEMICAL SOC
 
Date 2016-01-15T06:09:50Z
2016-01-15T06:09:50Z
2015
 
Type Article
 
Identifier JOURNAL OF PHYSICAL CHEMISTRY A, 119(30)8338-8348
1089-5639
http://dx.doi.org/10.1021/acs.jpca.5b06328
http://dspace.library.iitb.ac.in/jspui/handle/100/17896
 
Language en