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Abstract Reaction of {LiC6H2−2,4,6‐Cyp3⋅Et2O}2(Cyp=cyclopentyl) (1) of the new dispersion energy donor (DED) ligand, 2,4,6‐triscyclopentylphenyl with SnCl2afforded a mixture of the distannene {Sn(C6H2−2,4,6‐Cyp3)2}2(2), and the cyclotristannane {Sn(C6H2−2,4,6‐Cyp3)2}3(3).2is favored in solution at higher temperature (345 K or above) whereas3is preferred near 298 K. Van't Hoff analysis revealed the3to2conversion has a ΔH=33.36 kcal mol−1and ΔS=0.102 kcal mol−1 K−1, which gives a ΔG300 K=+2.86 kcal mol−1, showing that the conversion of3to2is an endergonic process. Computational studies show that DED stabilization in3is −28.5 kcal mol−1per {Sn(C6H2−2,4,6‐Cyp3)2unit, which exceeds the DED energy in2of −16.3 kcal mol−1per unit. The data clearly show that dispersion interactions are the main arbiter of the3to2equilibrium. Both2and3possess large dispersion stabilization energies which suppress monomer dissociation (supported by EDA results).
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Strong π-stacking causes unusually large anisotropic thermal expansion and thermochromism
π-stacking in ground-state dimers/trimers/tetramers ofN-butoxyphenyl(naphthalene)diimide (BNDI) exceeds 50 kcal ⋅ mol−1in strength, drastically surpassing that for the*3[pyrene]2excimer (∼30 kcal ⋅ mol−1; formal bond order = 1) and similar to other weak-to-moderate classical covalent bonds. Cooperative π-stacking in triclinic (BNDI-T) and monoclinic (BNDI-M) polymorphs effects unusually large linear thermal expansion coefficients (αa, αb, αc, β) of (452, −16.8, −154, 273) × 10−6⋅ K−1and (70.1, −44.7, 163, 177) × 10−6⋅ K−1, respectively. BNDI-T exhibits highly reversible thermochromism over a 300-K range, manifest by color changes from orange (ambient temperature) toward red (cryogenic temperatures) or yellow (375 K), with repeated thermal cycling sustained for over at least 2 y.
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- PAR ID:
- 10308270
- Publisher / Repository:
- Proceedings of the National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 118
- Issue:
- 44
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- Article No. e2106572118
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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