TY - JOUR
T1 - Structure–property relationship of dipyridyl−Cu polymers containing inorganic clusters Te/SeFe3(CO)9
AU - Shieh, Minghuey
AU - Li, Yu Huei
AU - Hsu, Ming Chi
N1 - Funding Information:
I thank the National Science and Technology Council of Taiwan for the continuous support of my research (NSTC; Grant 111‐2113‐M‐003‐017 to M. S.) and my present and former graduate students who have dedicated their time and talents to the work reported herein. We are also grateful to Prof. Hui‐Lung Chen (Chinese Culture University) for the assistance with DMol calculations and the National Synchrotron Radiation Research Center (NSRRC) of Taiwan for the XANES technical support. 3
Funding Information:
I thank the National Science and Technology Council of Taiwan for the continuous support of my research (NSTC; Grant 111-2113-M-003-017 to M. S.) and my present and former graduate students who have dedicated their time and talents to the work reported herein. We are also grateful to Prof. Hui-Lung Chen (Chinese Culture University) for the assistance with DMol3 calculations and the National Synchrotron Radiation Research Center (NSRRC) of Taiwan for the XANES technical support.
Publisher Copyright:
© 2023 The Chemical Society Located in Taipei & Wiley-VCH GmbH.
PY - 2023/5
Y1 - 2023/5
N2 - This mini-review covers a novel series of 1D and 2D Te/SeFe3(CO)9-incorporated (Te, 1a; Se, 1b) Cu-based coordination polymers synthesized by the liquid-assisted grinding (LAG) method using predesigned compound [TeFe3(CO)9Cu2(MeCN)2] (1a-Cu2(MeCN)2) with rigid or flexible dipyridyl ligands, or three components of [SeFe3(CO)9]2− (1b), [Cu(MeCN)4]+, and dipyridyls. These polymers displayed various cluster coordination modes, including cluster-blocked [EFe3(CO)9Cu2(L)]n (E = Te, 1a-L-1D, Se, 1b-L-1D; L = 1,2-bis(4-pyridyl)ethylene (bpee), 1,2-bis(4-pyridyl)ethane (bpea)), cluster-pendant [SeFe3(CO)9Cu2(dpy)3]n (1b-dpy-1D, dpy = 4,4′-dipyridyl) and [EFe3(CO)9Cu2(L)2.5]n (E = Te, 1a-L-2D, Se, 1b-L-2D; L = bpee, bpea), cluster-linked [SeFe3(CO)9Cu2(MeCN)(dpy)1.5]n (1b-dpy-2D) and [SeFe3(CO)9Cu2(bpp)2]n (1b-bpp-2D, bpp = 1,3-bis(4-pyridyl)propane), as well as the unique cation-anion polymer [{Cu2(bpp)4}{(TeFe3(CO)9Cu)2(bpp)}]n (1a-bpp-CA). Their dimensionality expansions and reversible transformations accompanied with bonding pattern changes were achieved upon the addition of stoichiometric amounts of appropriate agents. These polymers exhibited pronounced semiconducting properties with tunable energy gaps and optical (dc) or electrical conductivities. The trend of their semiconductivities can be related to bonding patterns, where efficient electron communications were proved to stem from the existence of carbonyl ligands and electron-rich clusters 1a and 1b. In particular, water−/light-stable 1b-based polymers exhibited excellent photodegradation activities toward nitroaromatics and organic dyes, where the efficiency was further rationalized by their structural features and narrow energy gaps.
AB - This mini-review covers a novel series of 1D and 2D Te/SeFe3(CO)9-incorporated (Te, 1a; Se, 1b) Cu-based coordination polymers synthesized by the liquid-assisted grinding (LAG) method using predesigned compound [TeFe3(CO)9Cu2(MeCN)2] (1a-Cu2(MeCN)2) with rigid or flexible dipyridyl ligands, or three components of [SeFe3(CO)9]2− (1b), [Cu(MeCN)4]+, and dipyridyls. These polymers displayed various cluster coordination modes, including cluster-blocked [EFe3(CO)9Cu2(L)]n (E = Te, 1a-L-1D, Se, 1b-L-1D; L = 1,2-bis(4-pyridyl)ethylene (bpee), 1,2-bis(4-pyridyl)ethane (bpea)), cluster-pendant [SeFe3(CO)9Cu2(dpy)3]n (1b-dpy-1D, dpy = 4,4′-dipyridyl) and [EFe3(CO)9Cu2(L)2.5]n (E = Te, 1a-L-2D, Se, 1b-L-2D; L = bpee, bpea), cluster-linked [SeFe3(CO)9Cu2(MeCN)(dpy)1.5]n (1b-dpy-2D) and [SeFe3(CO)9Cu2(bpp)2]n (1b-bpp-2D, bpp = 1,3-bis(4-pyridyl)propane), as well as the unique cation-anion polymer [{Cu2(bpp)4}{(TeFe3(CO)9Cu)2(bpp)}]n (1a-bpp-CA). Their dimensionality expansions and reversible transformations accompanied with bonding pattern changes were achieved upon the addition of stoichiometric amounts of appropriate agents. These polymers exhibited pronounced semiconducting properties with tunable energy gaps and optical (dc) or electrical conductivities. The trend of their semiconductivities can be related to bonding patterns, where efficient electron communications were proved to stem from the existence of carbonyl ligands and electron-rich clusters 1a and 1b. In particular, water−/light-stable 1b-based polymers exhibited excellent photodegradation activities toward nitroaromatics and organic dyes, where the efficiency was further rationalized by their structural features and narrow energy gaps.
KW - coordination polymer
KW - mechanochemical synthesis
KW - metal carbonyl cluster
KW - photodegradation
KW - semiconducting behavior
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U2 - 10.1002/jccs.202300054
DO - 10.1002/jccs.202300054
M3 - Review article
AN - SCOPUS:85150648366
SN - 0009-4536
VL - 70
SP - 984
EP - 991
JO - Journal of the Chinese Chemical Society
JF - Journal of the Chinese Chemical Society
IS - 5
ER -