Horizontal and Vertical Push Effects in Saddled Zinc Porphyrin Complexes: Implications for Heme Distortion

2019 ◽  
Vol 58 (4) ◽  
pp. 2627-2636 ◽  
Author(s):  
Jinjin Zhang ◽  
Min Tang ◽  
Dilong Chen ◽  
Binghua Lin ◽  
Zaichun Zhou ◽  
...  
2019 ◽  
Author(s):  
Simil Thomas ◽  
Hong Li ◽  
Raghunath R. Dasari ◽  
Austin Evans ◽  
William Dichtel ◽  
...  

<p>We have considered three two-dimensional (2D) π-conjugated polymer networks (i.e., covalent organic frameworks, COFs) materials based on pyrene, porphyrin, and zinc-porphyrin cores connected <i>via</i> diacetylenic linkers. Their electronic structures, investigated at the density functional theory global-hybrid level, are indicative of valence and conduction bands that have large widths, ranging between 1 and 2 eV. Using a molecular approach to derive the electronic couplings between adjacent core units and the electron-vibration couplings, the three π-conjugated 2D COFs are predicted to have ambipolar charge-transport characteristics with electron and hole mobilities in the range of 65-95 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup>. Such predicted values rank these 2D COFs among the highest-mobility organic semiconductors. In addition, we have synthesized the zinc-porphyrin based 2D COF and carried out structural characterization via powder X-ray diffraction and surface area analysis, which demonstrates the feasability of these electroactive networks.</p>


2021 ◽  
Author(s):  
Mandeep K. Chahal ◽  
Anuradha Liyanage ◽  
Ajyal Z. Alsaleh ◽  
Paul A. Karr ◽  
Jonathan P. Hill ◽  
...  

A new type of push–pull charge transfer complex, viz., a spiro-locked N-heterocycle-fused zinc porphyrin, ZnP-SQ, is shown to undergo excited state charge separation, which is enhanced by axial F− binding to the Zn center.


1988 ◽  
Vol 153 (4) ◽  
pp. 199-200 ◽  
Author(s):  
E. Mikros ◽  
A. Gaudemer ◽  
R. Pasternack

2003 ◽  
Vol 07 (03) ◽  
pp. 139-146 ◽  
Author(s):  
Peter Hambright ◽  
Ines Batinić-Haberle ◽  
Ivan Spasojević

The relative reactivities of the tetrakis( N -alkylpyridinium- X - yl )-porphyrins where X = 4 (alkyl = methyl, ethyl, n -propyl) , X = 3 (methyl) , and X = 2 (methyl, ethyl, n -propyl, n -butyl, n -hexyl, n -octyl) were studied in aqueous solution. From the ionic strength dependence of the metalation rate constants, the effective charge of a particular cationic porphyrin was usually larger when copper(II) rather than zinc(II) was the reactant. The kinetics of ZnOH + incorporation and the acid catalyzed removal of zinc from the porphyrins in 1.0 M HCl were also studied. In general, the more basic 4- (para-) and 3- (meta-) isomers were the most reactive, followed by the less basic 2- (ortho-) methyl to n -butyl derivatives, with the lipophilic ortho n -hexyl and n -octyl porphyrins the least reactive.


2007 ◽  
Vol 46 (19) ◽  
pp. 7749-7755 ◽  
Author(s):  
Yan-Qin Weng ◽  
Fan Yue ◽  
Yong-Rui Zhong ◽  
Bao-Hui Ye
Keyword(s):  

2009 ◽  
Vol 62 (7) ◽  
pp. 692 ◽  
Author(s):  
Toby D. M. Bell ◽  
Sheshanath V. Bhosale ◽  
Kenneth P. Ghiggino ◽  
Steven J. Langford ◽  
Clint P. Woodward

The synthesis of a porphyrin star-pentamer bearing a free-base porphyrin core and four zinc(ii) metalloporphyrins, which are tethered by a conformationally flexible linker about the central porphyrin’s antipody, is described. The synthetic strategy is highlighted by the use of olefin cross metathesis to link the five chromophores together in a directed fashion in high yield. Photoexcitation into the Soret absorption band of the zinc porphyrin chromophores at 425 nm leads to a substantial enhancement of central free-base porphyrin fluorescence, indicating energy transfer from the photoexcited zinc porphyrin (outer periphery) to central free-base porphyrin. Time-resolved fluorescence decay profiles required three exponential decay components for satisfactory fitting. These are attributed to emission from the central free-base porphyrin and to two different rates of energy transfer from the zinc porphyrins to the free-base porphyrin. The faster of these decay components equates to an energy-transfer rate constant of 3.7 × 109 s–1 and an efficiency of 83%, whereas the other is essentially unquenched with respect to reported values for zinc porphyrin fluorescence decay times. The relative contribution of these two components to the initial fluorescence decay is ~3:2, similar to the 5:4 ratio of cis and trans geometric isomers present in the pentamer.


2001 ◽  
Vol 105 (51) ◽  
pp. 11425-11431 ◽  
Author(s):  
Mikalai M. Yatskou ◽  
Rob B. M. Koehorst ◽  
Harry Donker ◽  
Tjeerd J. Schaafsma

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