Photophysical Studies on Covalently-linked Naphthalene and TEMPO Free Radical Systems: Observation of a Charge Transfer State in the Ground State.
A series of molecules containing a naphthalene chromophore and a stable free radical 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) covalently linked by a spacer group of different lengths have been synthesized. In n-hexane solution, their photophysical behavior was studied and compared with a system of freely moving naphthalene and the free radical TEMPO. The linked molecules showed strong quenching of the singlet and triplet states of the naphthalene moiety, compared to when naphthalene and TEMPO were not linked. The quenching efficiency decreased with increasing the length of the spacer group. In addition, new electronic absorption and emission bands, along with the usual bands of the individual moieties, were also seen. These news bands have been attributed to the formation of electron donor-acceptor charge-transfer complexes in the ground state, arising from the interaction between the two moieties in close proximity. The photophysical dynamics of the linked molecules has been rationalized by assuming the existence of two types of population of the linked molecules: folded and extended. The ground state complex formation is proposed to occur only in the folded conformation of the linked molecules. To our knowledge, this is possibly the first example of a ground state charge-transfer complex formation involving a TEMPO free radical and naphthalene.
Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai, 400005, India.
Vinayak
V
Rane
Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai, 400005, India.
Sushma
S
Kundu
Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai, 400005, India. ranjan@tifr.res.in.
Ranjan
R
Das
Charge transfer complex; Excited state quenching; Ground state charge transfer complex; Intramolecular quenching; Naphthalene; TEMPO