Quenching of singlet molecular oxygen by phthalocyanines and naphthalocyanines.
Quenching of singlet molecular oxygen by phthalocyanines and naphthalocyanines.
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酞菁和萘酞菁对单线态分子氧的猝灭。
DOI：
10.1111/j.1751-1097.1992.tb08512.x
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发表时间：
1992
影响因子：
3.3
通讯作者：
Lukjanetz,EA
中科院分区：
文献类型：
--
作者：
KrasnovskyJr,AA;Rodgers,MA;Galpern,MG;Rihter,B;Kenney,ME;Lukjanetz,EA
用直接测量单线态分子氧（~ 1 O_2）的光敏发光的方法，测定了下列酞菁和萘酞菁的单体分子在氯仿中对~ 1 O_2的猝灭速率常数（kq）：（4-叔丁基）酞菁⑴;八位数（3，6-丁氧基）酞菁（II），四-（6-叔丁基）-2，3-萘二甲酸（III）、四氢铝（1-叔-苯基）-2，3-萘二甲酸酯（IV）、硅-（V）、锡-（VI）、铝-（VII）和镓-（VIII）的三-（正己基-甲硅烷氧基）衍生物2，3-萘二甲酸酯。获得以下kq值（kq× 10- 8 M-1 s-1）：2.9（I），59（II），100（III），20（IV），3.9（V），53（VI），33（VII），110（VIII）。由于大多数猝灭剂具有低的三重态能级，因此分析了基于从1 O2到这些能级的能量转移的猝灭机制的贡献。提出了一个描述由该机理引起的kq值与猝灭剂三重态的物理常数之间关系的公式。将该公式应用于酞菁、萘菁、β-胡萝卜素和细菌叶绿素等化合物，结果表明，能量转移能充分解释V的活性，并对II、III和VI-VIII的活性有很大贡献。一个电荷转移相互作用可能是一个额外的机制参与1 O2猝灭的化合物研究。由于某些酞菁和萘酞菁是单线态氧的强物理猝灭剂，它们可用作光化学体系中光破坏过程的有效抑制剂。
Using the direct measurement of the photosensitized luminescence of singlet molecular oxygen (1O2) the rate constants (kq) have been determined for1O2quenching by the monomeric molecules of the following phthalocyanines and naphthalocyanines in chloroform: tetra‐(4‐tert‐butyl) phthalocyanine (I); octa‐(3,6‐butoxy) phthalocyanine (II), tetra‐(6‐tert‐butyl)‐2,3 naphthalocyanine (III), aluminium tetra‐(l‐tert‐phenyl)‐2,3 naphthalocyanine (IV), tri‐(n‐hexyl‐siloxy) derivatives of silicon‐(V), tin‐(VI), aluminium‐(VII) and gallium‐(VIII) 2,3 naphthalocyanine. The followingkqvalues were obtained (kq× 10–8M‐1s‐1): 2.9 (I), 59 (II), 100 (III), 20 (IV), 3.9 (V), 53 (VI), 33 (VII), 110 (VIII). As most of the quenchers have the low‐lying triplet levels, a contribution of the quenching mechanism based on the energy transfer from1O2to these levels has been analysed. A formula is proposed describing the relation betweenkqvalues caused by this mechanism, and photophysical constants of the quencher triplet state. This formula was applied to phthalocyanines, naphthalocyanines,p‐carotene and bacterochlorophylla.The data suggest that the energy transfer can fully explain the activity ofVand strongly contributes into the activities ofII,IIIandVI‐VIII. A charge transfer interaction might be an additional mechanism involved in1O2quenching by compounds studied. As some phthalocyanines and naphthalocyanines are strong physical quenchers of singlet oxygen they can be used as efficient inhibitors for photodestructive processes in photochemical systems.