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In the search of porphyrin arrays with a unique geometry, the efficient synthesis of a directly linked 21‐carba‐23‐thiaporphyrin dimer with the distinctive dihydrofulvalene bridging motif has been developed. This compound acquires an uncommon parallel‐displaced arrangement of two carbaporphyrin planes. The dimer undergoes an acid‐triggered cleavage to create of the asymmetric carbathiaporphyrin–carbathiachlorin...
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