Synthesis of β-substituted porphyrin building blocks and conversion to diphenylethyne-linked porphyrin dimers

被引:29
作者
Balasubramanian, T [1 ]
Lindsey, JS [1 ]
机构
[1] N Carolina State Univ, Dept Chem, Raleigh, NC 27695 USA
关键词
alkynes; orbital effects; porphyrins; pyrroles;
D O I
10.1016/S0040-4020(99)00339-7
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A recent hypothesis concerning effects of orbital ordering on electronic communication (excited-state energy transfer, ground-state hole-hopping) in covalently linked porphyrin arrays prompted the development and application of methodology for the synthesis of beta-linked porphyrin dimers. Reaction of a beta-substituted pyrrole with 2-hydroxymethylpyrrole led to the dipyrromethane bearing a single beta-substituent and no meso- nor alpha-substituents. Condensation of the beta-substituted dipyrromethane with an aldehyde and a meso-substituted dipyrromethane gave the desired beta-substituted porphyrin building block, albeit in low yield. Four building blocks were prepared with a p-iodophenyl or p-ethynylphenyl group at one beta-position, no substituent at the flanking meso-position, and mesityl or pentafluorophenyl groups at the three non-flanking meso-positions. The porphyrin building blocks were coupled via Pd-mediated reactions, affording diphenylethyne-linked dimers with the linker attached at beta-positions. This approach provided access to zinc-free base porphyrin dimers and bis-zinc dimers bearing mesityl or pentafluorophenyl groups at the three non-linking meso-positions. The availability of these dimers and monomeric benchmarks enabled a critical test of the orbital ordering hypothesis. This methodology for preparing porphyrin building blocks bearing a lone, non-hindered beta-substituent complements existing methods for preparing meso-substituted porphyrin building blocks. The ability to position the linker at the meso- or beta-positions provides a desirable level of versatility for incorporating porphyrinic molecules with an a(2u) or a(1u) HOMO in various molecular devices. (C) 1999 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:6771 / 6784
页数:14
相关论文
共 27 条
  • [11] ROTHEMUND AND ADLER-LONGO REACTIONS REVISITED - SYNTHESIS OF TETRAPHENYLPORPHYRINS UNDER EQUILIBRIUM CONDITIONS
    LINDSEY, JS
    SCHREIMAN, IC
    HSU, HC
    KEARNEY, PC
    MARGUERETTAZ, AM
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (05) : 827 - 836
  • [12] LITTLER BJ, IN PRESS J ORG CHEM
  • [13] Synthesis of linear amphipathic porphyrin dimers and trimers: An approach to bilayer lipid membrane spanning porphyrin arrays
    Nishino, N
    Wagner, RW
    Lindsey, JS
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (21) : 7534 - 7544
  • [14] INVESTIGATION OF ELECTRONIC COMMUNICATION IN MULTI-PORPHYRIN LIGHT-HARVESTING ARRAYS
    SETH, J
    PALANIAPPAN, V
    JOHNSON, TE
    PRATHAPAN, S
    LINDSEY, JS
    BOCIAN, DF
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (23) : 10578 - 10592
  • [15] Soluble synthetic multiporphyrin arrays .3. Static spectroscopic and electrochemical probes of electronic communication
    Seth, J
    Palaniappan, V
    Wagner, RW
    Johnson, TE
    Lindsey, JS
    Bocian, DF
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (45) : 11194 - 11207
  • [16] SRINIVASAN N, IN PRESS J PORPHYRIN
  • [17] Effects of orbital ordering on electronic communication in multiporphyrin arrays
    Strachan, JP
    Gentemann, S
    Seth, J
    Kalsbeck, WA
    Lindsey, JS
    Holten, D
    Bocian, DF
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (46) : 11191 - 11201
  • [18] Synthesis and characterization of tetrachlorodiarylethyne-linked porphyrin dimers. Effects of linker architecture on intradimer electronic communication
    Strachan, JP
    Gentemann, S
    Seth, J
    Kalsbeck, WA
    Lindsey, JS
    Holten, D
    Bocian, DF
    [J]. INORGANIC CHEMISTRY, 1998, 37 (06) : 1191 - 1201
  • [19] Tietze LF, 1996, SYNTHESIS-STUTTGART, P851
  • [20] VANLEUSEN AM, 1972, TETRAHEDRON LETT, P5337