Dibenzo[a,c]phenazine:: A polarity-insensitive hydrogen-bonding probe

被引:13
|
作者
Dey, Debarati [1 ]
Bose, Adity [1 ]
Bhattacharyya, Dhananjay [2 ]
Basu, Samita [1 ]
Maity, Shyam Sundar [3 ]
Ghosh, Sanjib [3 ]
机构
[1] Saha Inst Nucl Phys, Div Chem Sci, Kolkata 700064, India
[2] Saha Inst Nucl Phys, Div Biophys, Kolkata 700064, W Bengal, India
[3] Presidency Coll, Dept Chem, Kolkata 700073, India
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2007年 / 111卷 / 42期
关键词
D O I
10.1021/jp0731811
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A derivative of phenazine, dibenzo[a,c]phenazine (DBPZ), can be used as a very good hydrogen-bonding probe unlike its parent phenazine molecule. Steady-state absorption and fluorescence studies reveal that DBPZ is completely insensitive to polarity of the medium. However, DBPZ can form a hydrogen bond very efficiently in its first excited singlet state. The extent of this excited-state hydrogen-bond formation depends both on size and on hydrogen-bond donor ability of the solvents. Time-resolved fluorescence studies and theoretical calculations also suggest that this hydrogen-bond formation is much more favorable in the excited state as compared to the ground state. In the excited state, the electron density is pushed toward the nitrogen atoms from the benzene rings, thereby increasing the dipole moment of the DBPZ molecule. Although the dipole moment of DBPZ increases upon photoexcitation, like other polarity probes, the molecule remains fully insensitive to the polarity of the interacting solvent. This unusual behavior of DBPZ as compared to simple phenazine and other polarity probes is due to the structure of the molecule. Hydrogen atoms at the I and 8 positions of DBPZ are sterically interacting with a lone pair of electrons on the proximate nitrogen atoms and make both of the nitrogen atoms inaccessible to solvent molecules. For this reason, DBPZ cannot sense the polarity of the medium. However, DBPZ can only sense solvents, those that have hydrogen with some electropositive nature, that is, the hydrogen-bond donating solvents. Hydrogen being the smallest among all elements can only interact with the lone pair of electrons of nitrogen atoms. Thus, DBPZ can act as a sensor for the hydrogen-bond donating solvents irrespective of their dielectrics.
引用
收藏
页码:10500 / 10506
页数:7
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