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The dimeric self-assembly program of a new, multidentate ligand with cuprous ions overcomes crystal packing forces, which leads to Ci symmetry in the solid state, to form a no less than partially C2-symmetric structure in solution. The resulting tetranitro-substituted dicopper(I) metallocyclophane displays an exceptionally strong second harmonic frequency response (β = (3000 ± 600) × 10−30 esu for a fundamental at 800 nm).
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