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Our findings show how a structural change, which can be deformations along the layers, slipping of layers, or change of the interlayer distance, can induce metal-to-semiconductor or indirect-to-direct semiconductor transition, suggesting a way to adjust or even switch between the intralayer vs interlayer conductive anisotropy in Ni3(HITP)2, in particular, and 2D MOFs in general.The interfacial chemistry of diborane (B2H6) with hydroxylated silica was investigated via in situ Fourier-transform infrared spectroscopy and temperature-program