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Hexa Boron-Dipyrromethene Cyclotriphosphazenes: Synthesis, Crystal Structure, and Photophysical Properties

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Title Hexa Boron-Dipyrromethene Cyclotriphosphazenes: Synthesis, Crystal Structure, and Photophysical Properties
 
Creator RAO, MR
BOLLIGARLA, R
BUTCHER, RJ
RAVIKANTH, M
 
Subject capping coordination behavior
efficient energy-transfer
polymer building-blocks
x-ray structures
laser-dye pm567
copper(ii) complexes
organic nanodots
electrochemistry
spectroscopy
ligands
 
Description We have synthesized four examples of a cyclotriphosphazene ring appended with six boron-dipyrromethene dyes N(3)P(3)(BODIPY)(6) by adopting two different methods. In method I, 1 equiv of N(3)P(3)Cl(6) was treated with 6 equiv of meso-(o(-) or m- or p-hydroxyphenyl)boron-dipyrromethene in tetrahydrofuran (THF) in the presence of cesium carbonate. This afforded N(3)P(3)(BODIPY)(6) in yields ranging from 80 to 90%. In method II, we first prepared hexakis(p-formylphenoxy)cyclotriphosphazene N(3)P(3)(CHO)(6) by treating 1 equiv of N(3)P(3)Cl(6) with 6 equiv of 4-hydroxybenzaldehyde in the presence of cesium carbonate in THF. In the second step, N(3)P(3)(CHO)(6) was condensed with excess of pyrrole in the presence of catalytic amount of trifluoroacetic acid (TFA) in CH(2)Cl(2) at room temperature and afforded hexakis(p-phenoxy dipyrromethane)cyclotriphosphazene. In the last step, the hexakis(p-phenoxy dipyrromethane)cyclotriphosphazene was first oxidized with 6 equiv of DDQ in CH(2)Cl(2) at room temperature for 1 h followed by neutralization with triethylamine and further reaction with excess BF(3)center dot Et(2)O afforded the target N(3)P(3)(BODIPY)(6) in 16% yield. The route II was used only for the synthesis of one target compound whereas the route I was used for the synthesis of all four target compounds. The four compounds were characterized by mass, NMR, absorption, electrochemical, and fluorescence techniques. The crystal structure solved for one of the compounds revealed That the P(3)N(3) ring is slightly puckered and the six substituents were not interacting with each other and attained pseudo-axial and pseudo-equatorial positions. The photophysical studies in five different solvents indicated that the compounds exhibit large Stokes' shifts unlike reference monomeric BODIPYs indicating that the compounds are promising for fluorescence bioassays. The quantum yields and lifetimes of compounds 1-4 depends on the type of BODIPY unit attached to the cyclotriphosphazene ring.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-14T06:39:55Z
2011-12-26T12:48:14Z
2011-12-27T05:47:02Z
2011-07-14T06:39:55Z
2011-12-26T12:48:14Z
2011-12-27T05:47:02Z
2010
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 49(22), 10606-10616
0020-1669
http://dx.doi.org/10.1021/ic1016092
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3883
http://hdl.handle.net/10054/3883
 
Language en