Impact of metallophilicity on “colossal” positive and negative thermal expansion in a series of isostructural dicyanometallate coordination polymers

JL Korcok, MJ Katz, DB Leznoff - Journal of the American …, 2009 - ACS Publications
JL Korcok, MJ Katz, DB Leznoff
Journal of the American Chemical Society, 2009ACS Publications
Five isostructural dicyanometallate coordination polymers containing metallophilic
interactions (In [M (CN) 2] 3 (M= Ag, Au), KCd [M (CN) 2] 3, and KNi [Au (CN) 2] 3) were
synthesized and investigated by variable-temperature powder X-ray diffraction to probe their
thermal expansion properties. The compounds have a trigonal unit cell and show positive
thermal expansion (PTE) in the ab plane, where Kagome sheets of M atoms reside, and
negative thermal expansion (NTE) along the trigonal c axis, perpendicular to these sheets …
Five isostructural dicyanometallate coordination polymers containing metallophilic interactions (In[M(CN)2]3 (M = Ag, Au), KCd[M(CN)2]3, and KNi[Au(CN)2]3) were synthesized and investigated by variable-temperature powder X-ray diffraction to probe their thermal expansion properties. The compounds have a trigonal unit cell and show positive thermal expansion (PTE) in the ab plane, where Kagome sheets of M atoms reside, and negative thermal expansion (NTE) along the trigonal c axis, perpendicular to these sheets. The magnitude of thermal expansion is unusually large in all cases (40 × 10−6 K−1 < |α| < 110 × 10−6 K−1). The system with the weakest metallophilic interactions, In[Ag(CN)2]3, shows the most “colossal” thermal expansion of the series (αa = 105(2) × 10−6 K−1, αc = −84(2) × 10−6 K−1 at 295 K), while systems containing stronger Au−Au interactions show relatively reduced thermal expansion. Thus, it appears that strong metallophilic interactions hinder colossal thermal expansion behavior. Additionally, the presence of K+ counterions also reduces the magnitude of thermal expansion.
ACS Publications
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