Under identical conditions, CuI reacts with PhS(CH2 )8 SPh and p-TolS(CH2 )8 STol-p affording, respectively, a luminescent 1D coordination polymer [Cu4 I4 {μ2 -PhS(CH2 )8 SPh}2 ]n (1) and an unprecedented 2D network [Cu8 I8 {μ2 -p-TolS(CH2 )8 STol-p}3 (MeCN)2 ]n (2), which incorporate closed-cubane Cu4 I4 and octanuclear Cu8 I8 clusters of as connecting nodes. Their thermal and photophysical properties exhibit notable differences.
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