A Convergent Synthetic Approach Using Sterically Demanding Aryldipyrrylmethanes for Tuning the Pocket Sizes of Cofacial Bisporphyrins
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- 作者：Christopher J. Chang ; Yongqi Deng ; Shie-Ming Peng ; Gene-Hsiang Lee ; Chen-Yu Yeh ; and Daniel G. Nocera
- 刊名：Inorganic Chemistry
- 出版年：2002
- 出版时间：June 3, 2002
- 年：2002
- 卷：41
- 期：11
- 页码：3008 - 3016
- 全文大小：110K
- 年卷期：v.41,no.11(June 3, 2002)
- ISSN：1520-510X
文摘
Meso substitution opposite to the spacer provides a convenient approach for tuning the pocket sizes of pillaredcofacial bisporphyrins. The synthesis and coordination chemistry of xanthene and dibenzofuran anchored platformsstructurally modified with 2,6-dimethoxyaryl groups are described. Comparative structural analysis of xanthenederivatives confirms the ability of the trans-aryl groups to adjust the vertical dimension of the cofacial cleft: 7(C97H106Cl4N8O5), monoclinic, space group P21/c, a = 28.8353(12) Å, b = 17.1139(7) Å, c = 17.5978(7) Å, 
=98.826(1)
, Z = 4; 8 (C101H123Cl2N8O11.5Zn2), monoclinic, space group P21/n, a = 14.5517(6) Å, b = 22.9226(10)Å, c = 28.5155(13) Å, = 90.312(14), Z = 4; 12 (C99H102Cl14N8O5Mn2), monoclinic, space group P2/c, a =19.5891(3) Å, b = 15.0741(2) Å, c = 33.2019(6) Å, = 91.947(10), Z = 4. The convenience and versatility ofthis synthetic method offers intriguing opportunities to specifically tailor the binding pockets of cofacial bisporphyrinsfor the study of small-molecule activation within a proton-coupled electron transfer framework.
=98.826(1), Z = 4; 8 (C101H123Cl2N8O11.5Zn2), monoclinic, space group P21/n, a = 14.5517(6) Å, b = 22.9226(10)Å, c = 28.5155(13) Å, = 90.312(14), Z = 4; 12 (C99H102Cl14N8O5Mn2), monoclinic, space group P2/c, a =19.5891(3) Å, b = 15.0741(2) Å, c = 33.2019(6) Å, = 91.947(10), Z = 4. The convenience and versatility ofthis synthetic method offers intriguing opportunities to specifically tailor the binding pockets of cofacial bisporphyrinsfor the study of small-molecule activation within a proton-coupled electron transfer framework.