TY - JOUR
T1 - Single-Crystal-to-Single-Crystal Transformation of Hydrogen-Bonded Triple-Stranded Ladder Coordination Polymer via Photodimerization Reaction
AU - Al-Mohsin, Hasan Ali
AU - Almousa, Ammar
AU - Oladepo, Sulayman A.
AU - Jalilov, Almaz S.
AU - Fettouhi, Mohammed
AU - Peedikakkal, Abdul Malik P.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/8/5
Y1 - 2019/8/5
N2 - A one-dimensional hydrogen-bonded triple-stranded ladder coordination polymer [Cd(bpe)1.5(NO3)2(H2O)] (1) (where bpe = trans-1,2-bis(4-pyridyl)ethylene) containing three parallel C=C double bonds was synthesized. This compound undergoes photochemical [2 + 2] cycloaddition and produces rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) in up to 67% yield via Single-Crystal-to-Single-Crystal (SCSC) transformation. Triple-stranded ladder-like structures have never before displayed such a kind of SCSC transformation. Furthermore, photoirradiation of ground 1 produces rctt-tpcb in up to 100% yield in the solid state. On the basis of the alignment of three C=C olefinic bonds of bpe ligands in parallel, only two out of the three aligned bpe are expected to undergo [2 + 2] photodimerization. However, the quantitative yield from the solid-state photochemical [2 + 2] cycloaddition reaction has been achieved via grinding of crystals of 1 to a powder. The effects of grinding on photoreactivity of 1 were thoroughly studied using 1H NMR spectroscopy, thermogravimetric analysis (TGA), and Raman spectroscopy. These studies indicate that the molecular movements of the hydrogen-bonded ladders are reinforced due to the loss of coordinated water molecules and the further crystal repacking via bond-breaking/forming of the hydrogen-bonded assemblies during mechanical grinding. The 100% photodimerization of ground 1 shows that the grinding accelerates internal molecular motions of ladder structures within the crystals lattice. The solid-state photoluminescence of 1, before and after UV irradiation, was investigated at room temperature, both indicative of interesting luminescent properties.
AB - A one-dimensional hydrogen-bonded triple-stranded ladder coordination polymer [Cd(bpe)1.5(NO3)2(H2O)] (1) (where bpe = trans-1,2-bis(4-pyridyl)ethylene) containing three parallel C=C double bonds was synthesized. This compound undergoes photochemical [2 + 2] cycloaddition and produces rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) in up to 67% yield via Single-Crystal-to-Single-Crystal (SCSC) transformation. Triple-stranded ladder-like structures have never before displayed such a kind of SCSC transformation. Furthermore, photoirradiation of ground 1 produces rctt-tpcb in up to 100% yield in the solid state. On the basis of the alignment of three C=C olefinic bonds of bpe ligands in parallel, only two out of the three aligned bpe are expected to undergo [2 + 2] photodimerization. However, the quantitative yield from the solid-state photochemical [2 + 2] cycloaddition reaction has been achieved via grinding of crystals of 1 to a powder. The effects of grinding on photoreactivity of 1 were thoroughly studied using 1H NMR spectroscopy, thermogravimetric analysis (TGA), and Raman spectroscopy. These studies indicate that the molecular movements of the hydrogen-bonded ladders are reinforced due to the loss of coordinated water molecules and the further crystal repacking via bond-breaking/forming of the hydrogen-bonded assemblies during mechanical grinding. The 100% photodimerization of ground 1 shows that the grinding accelerates internal molecular motions of ladder structures within the crystals lattice. The solid-state photoluminescence of 1, before and after UV irradiation, was investigated at room temperature, both indicative of interesting luminescent properties.
UR - http://www.scopus.com/inward/record.url?scp=85070911482&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b01276
DO - 10.1021/acs.inorgchem.9b01276
M3 - Article
C2 - 31317737
AN - SCOPUS:85070911482
SN - 0020-1669
VL - 58
SP - 10167
EP - 10173
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 15
ER -