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首页> 外文期刊>Chemistry: A European journal >Triplet-triplet energy transfer controlled by the donor-acceptor distance in rigidly held palladium-containing cofacial bisporphyrins
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Triplet-triplet energy transfer controlled by the donor-acceptor distance in rigidly held palladium-containing cofacial bisporphyrins

机译：三重态-三重态能量传递受刚性持有的含钯界面双卟啉中供体-受体距离的控制

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摘要

Eleven new complexes, including mono-, heterobi-, and homobimetallic cofacial bisporphyrins, (Pd)H2DPS, (M)H2DPX, (M)H2DPB, (PdZn)DPS, (PdZn)DPX, (Pt)(2)DPX, (M)(2)DPB (M=Pd, Pt), and (Pt)P (DPS4- = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]di- benzothiophene tetraanion, DPX4-= 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphlrinvl)]-9,9-dimethyl-xanthene tetraanion, DPB4- = 1,8-bis[5(2,8,13,17-tetraethyl-3,7,12,18-tetrame- thylporphyrinyl)]biphenylene tetraanion, P2-=5-phenyl-2,8,13,17-tetraethvl-3,7,12,18-tetramethylporphyin dianion) have been synthesized and characterized. The photophysical properties of the donor (M)P (M=Pd or Pt, P= porphyrin chromophore) and the acceptor (free base H2P or (Zn)P) depend on the C-meso - C-meso distance and the presence of a heavy atom such as Pd-II or Pt-II. The data were compared with those for the known compounds (Pd)(2)DPS, (Pd)(2)DPX, H4DPS, H4DPX, H4DPB, (Pd)P, (Zn)P, and H2P The rate constants for triplet-triplet energy transfer (k(ET)) were measured for the heterobimetallic (PdZn) and monometallic [(M)H-2] derivatives (M=Pd, Pt). The fluorescence lifetimes (Delta tau(F)) of the acceptors decrease as a result of the heavy-atom effect, and vary as follows: (Pd)H2DPS < (Pd)H2DPX-(Pd)H2DPB. The k(ET) values calculated according to the equation k(ET) = (1/tau(emi) - 1/tau(emi)(0)), where tau(emi)(0) is the emission lifetime of the homobimetallic bisporphyrins (no ET occurs), are equal to 0, 247 +/- 57 and 133 +/- 52 s(-1) for DPS, DPX, and DPB, respectively, in the (Pd)H-2 series. These measurements allowed the range of distance over which the Dexter mechanism for T-1-T-1 energy transfer ceases to operate to be determined. This distance is somewhere between 4.3 and 6.3 A, in agreement with our recent findings on singlet-singlet energy transfer. During the course of this study, the X-ray crystal structure for (Pd)H,DPX was obtained; triclinic (P1), a = 11.1016(1), b = 14.9868(2), c = 20.6786(3) A, alpha = 102.091(1), beta =100.587(1), gamma 101.817(1)degrees, V = 3199.19(7) A(3), Z = 2.
机译：十一种新的配合物，包括单金属，杂双金属和同金属双界面双卟啉，（Pd）H2DPS，（M）H2DPX，（M）H2DPB，（PdZn）DPS，（PdZn）DPX，（Pt）（2）DPX，（ M）（2）DPB（M = Pd，Pt）和（Pt）P（DPS4- = 4,6-双[5-（2,8,13,17-四乙基-3,7,12,18-四甲基卟啉基）]-二苯并噻吩四阴离子，DPX4- = 4,5-双[5-（2,8,13,17-四乙基-3,7,12,18-四甲基卟啉 lrinvl）]-9,9-二甲基- an吨四阴离子，DPB4- = 1,8-双[5（2,8,13,17-四乙基-3,7,12,18-四甲基卟啉基）]联苯四阴离子，P2- = 5-苯基-2,8 （13,17-tetraethvl-3,7,12,18-tetramethylporphyin dianion）已经合成并表征。供体（M）P（M = Pd或Pt，P =卟啉发色团）和受体（游离碱H2P或（Zn）P）的光物理性质取决于C-meso-C-meso距离和重原子，例如Pd-II或Pt-II。将该数据与已知化合物（Pd）（2）DPS，（Pd）（2）DPX，H4DPS，H4DPX，H4DPB，（Pd）P，（Zn）P和H2P的数据进行比较。测量了异双金属（PdZn）和单金属[（M）H-2]衍生物（M = Pd，Pt）的三重态能量转移（k（ET））。由于重原子效应，受体的荧光寿命（Delta tau（F））减少，并且变化如下：（Pd）H2DPS <（Pd）H2DPX-（Pd）H2DPB。根据方程式k（ET）=（1 / tau（emi）-1 / tau（emi）（0））计算的k（ET）值，其中tau（emi）（0）是同双金属的发射寿命（Pd）H-2系列中的DPS，DPX和DPB的双卟啉（无ET发生）分别等于0、247 +/- 57和133 +/- 52 s（-1）。这些测量结果确定了用于T-1-T-1能量转移的Dexter机构停止工作的距离范围。这个距离在4.3和6.3 A之间，这与我们最近关于单重态-单重态能量转移的发现一致。在研究过程中，获得了（Pd）H，DPX的X射线晶体结构。三斜晶（P1），a = 11.1016（1），b = 14.9868（2），c = 20.6786（3）A，alpha = 102.091（1），beta = 100.587（1），伽马101.817（1）度，V = 3199.19（7）A（3），Z = 2

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