Non planar 14 -π aromatic subphthalocyanine has been introduced for the first time as hole transporting material for organometal halide perovskite solar cells and achieved a power conversion efficiency of 6.6%. Cells stored in the dark under ambient conditions underwent an incubation period of nine days during which, we observed an increase in efficiency followed by slow progressive deterioration. However, Raman spectral analysis of pristine perovskite deposited on titania revealed a much faster degradation thus indicating that the subphthalocyanine layer provides a temporary protection to the underlying perovskite layer.The Raman spectra of PbCl 2 and CH 3 NH 3 I precursors are given in Figure 7. Both spectra were collected under inert atmosphere. The Raman spectrum of the CH 3 NH 3 PbCl x I 3-x perovskite at ambient conditions is also given in the same figure for comparison. It was collected using 0.8 mW laser power, which is a considerably high value for photosensitive materials. The peaks at 515, 397 and 144 cm -1 are attributed to TiO 2 (anatase) substrate and the fact that they appear in the spectrum suggests that the laser power is adequate for the photons to reach the substrate and the inelastically scattered light subsequently to reach the
Macrocyclic compounds generally possess flexible skeletons, which results in them having a variety of conformations or molecular shapes. In the case of macrocycles with p systems, the conformation governs their electronic states, as well as their reactivity. As a result of the recent developments in the synthesis of expanded porphyrins, [1] many studies of the relationships between their conformations and electronic properties have been reported. [2] Peripheral modification of expanded porphyrins to construct rigid frameworks have also been investigated. [3] Importantly, expanded porphyrins purely composed of regular pyrroles (connected to the meso-carbon atoms at the a,a'-positions) are often less stable or in a metastable state, and undergo skeletal transformation induced by external stimuli. In particular, metal coordination can trigger unique skeletal transformations. For example, heptaphyrins and octaphyrins were split in two upon metal coordination. [4,5] A notable example of such a skeletal transformation is a "confusion reaction", for example, the conversion of a regular hexaphyrin into doubly N-confused dioxohexaphyrin through oxidative copper metalation. [6] The results of this particular reaction suggest that N-confused pyrroles (connected to the meso-carbon atoms at the a,b'positions) would stabilize the skeleton of expanded porphyrins. Herein, we describe a palladium-induced unique skeletal rearrangement from a singly N-confused hexaphyrin to a doubly N-confused hexaphyrin, to give a bis(Pd II ) complex of doubly N-confused [26]hexaphyrin 2 with a markedly decreased HOMO-LUMO band gap of less than 1 eV. This is the first example of organometallic doubly N-confused hexaphyrin complexes and of a cis-configured doubly Nconfused hexaphyrin.The palladium-induced skeletal rearrangement reaction was discovered during a study on palladium coordination chemistry of the singly N-confused [26]hexaphyrin 1 (Scheme 1 a). [7] A solution of 1 and 5 equivalents of PdCl 2 in acetonitrile was heated at reflux for 30 min and, after the usual workup and chromatographic separation, the bis(Pd II ) complex of doubly N-confused [26]hexaphyrin 2 was isolated in 24 % yield. Complex 2 was stable both as a solid and in solution under ambient conditions. The laser desorption/ ionization mass spectrum of 2 displayed the parent ion signal around m/z = 1670, thus indicating that it could be the bis(Pd) complex. The 1 H NMR and 19 F NMR spectra of 2 in CDCl 3 at room temperature suggest a C s symmetric structure. A singlet signal assignable to the b-CH of N-confused pyrrole rings was observed at d = 8.80 ppm (2 H). In the 1 H NMR spectrum, a pair of doublet signals corresponding to two regular pyrrole rings appeared at 8.34 and 8.25 ppm (both 2 H, J = 4.9 Hz) and a singlet signal corresponding to the remaining two regular pyrrole rings appeared at 8.50 ppm (4 H). Signals for six meso-C 6 F 5 groups are observed in a 2:2:1:1 ratio, thus supporting the C s symmetric structure. [8] When the reaction of 1 was performed with 1 equiva...
An expanded metalloporphyrin-based "black dye" Au−Pd oxohexaphyrin (AuPd-1) with absorption capabilities across the visible-to-near-infrared (NIR) range was synthesized. This black dye, AuPd-1, possessed efficient light-harvesting and photostable capabilities, which were indicative of superior photothermal (PT) conversion abilities. Encapsulation of AuPd-1 with a micellar nanocapsule resulted in a compound that demonstrated intense photoacoustic (PA) properties in the NIR region in water. This finding indicated how metal (d)−ligand (π) molecular orbital interactions in metalloporphyrins could aid in the design of visible-to-NIR lightharvesting black dyes for PT and PA applications.
Mix and match: The title porphyrinoid has been synthesized and shows unique coordination chemistry by incorporating two different metals with different oxidation states (see figure). X‐ray crystallography was used to confirm that a rectangular conformation in both mono‐ and binuclear complexes was retained.
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