TY - JOUR
T1 - Excited-State Energy-Transfer Dynamics of Self-Assembled Imine-Linked Porphyrin Dyads
AU - Sazanovich, Igor V.
AU - Balakumar, Arumugham
AU - Muthukumaran, Kannan
AU - Hindin, Eve
AU - Kirmaier, Christine
AU - Diers, James R.
AU - Lindsey, Jonathan S.
AU - Bocian, David F.
AU - Holten, Dewey
PY - 2003/10/20
Y1 - 2003/10/20
N2 - Toward the development of new strategies for the synthesis of multiporphyrin arrays, we have prepared and characterized (electrochemistry and static/time-resolved optical spectroscopy) a series of dyads composed of a zinc porphyrin and a free base porphyrin joined via imine-based linkers. One dyad contains two zinc porphyrins. Imine formation occurs under gentle conditions without alteration of the porphyrin metalation state. Five imine linkers were investigated by combination of formyl, benzaldehyde, and salicylaldehyde groups with aniline and benzoic hydrazide groups. The imine-linked dyads are quite stable to routine handling. The excited-state energy-transfer rate from zinc to free base porphyrin ranges from (70 ps)-1 to (13 ps)-1 in toluene at room temperature depending on the linker employed. The energy-transfer yield is generally very high (>97%), with low yields of deleterious hole/electron transfer. Collectively, this work provides the foundation for the design of multiporphyrin arrays that self-assemble via stable imine linkages, have predictable electronic properties, and have comparable or even enhanced energy-transfer characteristics relative to those of other types of covalently linked systems.
AB - Toward the development of new strategies for the synthesis of multiporphyrin arrays, we have prepared and characterized (electrochemistry and static/time-resolved optical spectroscopy) a series of dyads composed of a zinc porphyrin and a free base porphyrin joined via imine-based linkers. One dyad contains two zinc porphyrins. Imine formation occurs under gentle conditions without alteration of the porphyrin metalation state. Five imine linkers were investigated by combination of formyl, benzaldehyde, and salicylaldehyde groups with aniline and benzoic hydrazide groups. The imine-linked dyads are quite stable to routine handling. The excited-state energy-transfer rate from zinc to free base porphyrin ranges from (70 ps)-1 to (13 ps)-1 in toluene at room temperature depending on the linker employed. The energy-transfer yield is generally very high (>97%), with low yields of deleterious hole/electron transfer. Collectively, this work provides the foundation for the design of multiporphyrin arrays that self-assemble via stable imine linkages, have predictable electronic properties, and have comparable or even enhanced energy-transfer characteristics relative to those of other types of covalently linked systems.
UR - https://www.scopus.com/pages/publications/0142092643
U2 - 10.1021/ic034558u
DO - 10.1021/ic034558u
M3 - Article
AN - SCOPUS:0142092643
SN - 0020-1669
VL - 42
SP - 6616
EP - 6628
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -