Reactivity of CuI and CuBr toward Dialkyl Sulfides
RSR: From Discrete Molecular Cu<sub>4</sub>I<sub>4</sub>S<sub>4</sub> and Cu<sub>8</sub>I<sub>8</sub>S<sub>6</sub> Clusters to Luminescent
Copper(I) Coordination Polymers
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Abstract
The 1D coordination polymer (CP)
[(Me<sub>2</sub>S)<sub>3</sub>{Cu<sub>2</sub>(μ-I)<sub>2</sub>}]<sub><i>n</i></sub> (<b>1</b>) is formed when CuI
reacts with SMe<sub>2</sub> in <i>n</i>-heptane, whereas
in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me<sub>2</sub>S)<sub>3</sub>{Cu<sub>4</sub>(μ-I)<sub>4</sub>}]<sub><i>n</i></sub> (<b>2</b>) containing “flower-basket”
Cu<sub>4</sub>I<sub>4</sub> units. The reaction product of CuI with
MeSEt is also solvent-dependent, where the 1D polymer [(MeSEt)<sub>2</sub>{Cu<sub>4</sub>(μ<sub>3</sub>-I)<sub>2</sub>(μ<sub>2</sub>-I)<sub>2</sub>}(MeCN)<sub>2</sub>]<sub><i>n</i></sub> (<b>3</b>) containing “stepped-cubane” Cu<sub>4</sub>I<sub>4</sub> units is isolated in MeCN. In contrast, the reaction
in <i>n</i>-heptane affords the 1D CP [(MeSEt)<sub>3</sub>{Cu<sub>4</sub>(μ<sub>3</sub>-I)<sub>4</sub>}]<sub><i>n</i></sub> (<b>4</b>) containing “closed-cubane”
Cu<sub>4</sub>I<sub>4</sub> clusters. The reaction of MeSPr with CuI
provides the structurally related 1D CP [(MeSPr)<sub>3</sub>{Cu<sub>4</sub>(μ<sub>3</sub>-I)<sub>4</sub>}]<sub><i>n</i></sub> (<b>5</b>), for which the X-ray structure has been determined
at 115, 155, 195, 235, and 275 K, addressing the evolution of the
metric parameters. Similarly to <b>4</b> and the previously
reported CP [(Et<sub>2</sub>S)<sub>3</sub>{Cu<sub>4</sub>(μ<sub>3</sub>-I)<sub>4</sub>}]<sub><i>n</i></sub> (<i>Inorg.
Chem.</i> <b>2010</b>, <i>49</i>, 5834), the
1D chain is built upon closed cubanes Cu<sub>4</sub>(μ<sub>3</sub>-I)<sub>4</sub> as secondary building units (SBUs) interconnected
via μ-MeSPr ligands. The 0D tetranuclear clusters [(L)<sub>4</sub>{Cu<sub>4</sub>(μ<sub>3</sub>-I)<sub>4</sub>}] [L = EtSPr (<b>6</b>), Pr<sub>2</sub>S (<b>7</b>)] respectively result
from the reaction of CuI with EtSPr and <i>n</i>-Pr<sub>2</sub>S. With <i>i</i>-Pr<sub>2</sub>S, the octanuclear
cluster [(<i>i</i>-Pr<sub>2</sub>S)<sub>6</sub>{Cu<sub>8</sub>(μ<sub>3</sub>-I)<sub>3</sub>}(μ<sub>4</sub>-I)<sub>2</sub>}] (<b>8</b>) is formed. An X-ray study has also been performed
at five different temperatures for the 2D polymer [(Cu<sub>3</sub>Br<sub>3</sub>)(MeSEt)<sub>3</sub>]<sub><i>n</i></sub> (<b>9</b>) formed from the reaction between CuBr and MeSEt in heptane.
The unprecedented framework of <b>9</b> consists of layers with
alternating Cu(μ<sub>2</sub>-Br)<sub>2</sub>Cu rhomboids, which
are connected through two μ-MeSEt ligands to tetranuclear open-cubane
Cu<sub>4</sub>Br<sub>4</sub> SBUs. MeSPr forms with CuBr in heptane
the 1D CP [(Cu<sub>3</sub>Br<sub>3</sub>)(MeSPr)<sub>3</sub>]<sub><i>n</i></sub> (<b>10</b>), which is converted to
a 2D metal–organic framework [(Cu<sub>5</sub>Br<sub>5</sub>)(μ<sub>2</sub>-MeSPr)<sub>3</sub>]<sub><i>n</i></sub> (<b>11</b>) incorporating pentanuclear [(Cu<sub>5</sub>(μ<sub>4</sub>-Br)(μ<sub>2</sub>-Br)] SBUs when recrystallized in
MeCN. The thermal stability and photophysical properties of these
materials are also reported
