收稿日期：2020⁃05⁃20。收修改稿日期：2020⁃11⁃02。
国家自然科学基金(No.21763028)、延安大学科研计划项目(No.YDY2017⁃07)、国家级大学生创新创业训练计划项目(No.201910719025)和陕西省教育厅重点科学研究计划项目(No.20JS154)资助。
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通信联系人。E⁃mail ：*********************
第37卷第2期2021年2月Vol.37No.2340⁃350
无机化学学报
CHINESE JOURNAL OF INORGANIC CHEMISTRY
基于三联吡啶/苯三羧酸类配体构筑的两个配合物的合成、结构和性质
陈小莉＊商璐黄梦萍童钰庆张佳楠薛万年
(延安大学化学与化工学院，陕西省反应工程重点实验室，新能源新功能材料实验室，延安
716000)
摘要：基于H 3tbtd 、H 3bbta 和bpy 配体在水热条件下合成了配位聚合物{[Co 3(tbtd)2(bpy)2(H 2O)]·5H 2O}n (1)和配合物[Cd 2(Hbbta)
(bpy)3(C 2O 4)(H 2O)](2)(H 3tbtd=4⁃(2，
4，6⁃三羧基苯基)⁃2，2′，6′，2″⁃三联吡啶，H 3bbta=1⁃氟⁃2，4，6⁃苯三酸，bpy=2，2′⁃联吡啶)，并用元素分析、红外光谱、X 射线单晶衍射等对其进行了表征。配聚物1为二维网状结构，基于丰富的氢键作用扩展形成三维超分子网结构。配合物2为双核结构，相邻的双核结构通过吡啶环之间的π…π堆积作用和氢键作用扩展为二维超分子网状结构。配聚物1在紫外光照射下对染料甲基橙(MO)的降解具有光催化活性，对紫外光催化具有良好的稳定性。此外还研究了配合物2的荧光性质和配合物1~2的热稳定性。
关键词：4⁃(2，4，6⁃三羧基苯基)⁃2，2′，6′，2″⁃三联吡啶；1⁃氟⁃2，4，6⁃苯三酸；晶体结构；荧光；光催化中图分类号：O614.81+2；O614.24+2文献标识码：A
文章编号：1001⁃4861(2021)02⁃0340⁃11
DOI ：10.11862/CJIC.2021.037
Two Complexes Based on Terpyridine/Benzotricarboxylic Acid Ligands:Synthesis,Structures and Properties
CHEN Xiao⁃Li ＊
SHANG Lu
HUANG Meng⁃Ping
TONG Yu⁃Qing
ZHANG Jia⁃nan
XUE Wan⁃Nian
(S chool of Chemistry and Chemical Engineering,Shaanxi Key Laboratory of Chemical Reaction Engineering,Laboratory of New Energy &New Function Materials,Yanan University,Yan′an,Shaanxi 716000,China )
Abstract:A coordination polymer (CP)and a complex based on H 3tbtd/H 3bbta and bpy ligands,namely {[Co 3(tbtd)2(bpy)2(H 2O)]·5H 2O}n (1)and [Cd 2(Hbbta)(bpy)3(C 2O 4)(H 2O)](2)(H 3tbtd=4⁃(2,4,6⁃tricarboxylphenyl)⁃2,2′,6′,2″⁃terpyri⁃
dine,H 3bbta=1⁃fluoro⁃2,4,6⁃phenyltriacid,bpy=2,2′⁃dipyridine),have been hydrothermal synthesized and structur⁃ally characterized by elemental analyses,IR spectroscopy and single⁃crystal X⁃ray diffraction analyses.1shows 2D network structure,which is linked into 3D supramolecular network through intermolecular hydrogen bonding inter⁃actions.2is binuclear structure,which is linked by π…πstack interactions and hydrogen bonding interactions to form 2D supramolecular network.CP 1exhibited photocatalytic activities for degradation of methyl orange (MO)un⁃
der UV light irradiation and showed good stabilities toward UV⁃light photocatalysis.In addition,luminescence prop⁃
erty of 2and thermal stabilities of 1~2were also studied.CCDC:1986403,1,2004223,2.
Keywords:4⁃(2,4,6⁃tricarboxylphenyl)⁃2,2′,6′,2″⁃terpyridine;1⁃fluoro⁃2,4,6⁃phenyltriacid;crystal structure;luminescence;
photocatalysis
第2期0Introduction
The crystal engineering of coordination polymers
(CPs)has attracted extensive attention because control⁃ling the molecular organization in the solid state can lead to materials with intriguing structural motifs and promising properties in luminescence sensing,magne⁃tism,catalysis,gas absorption,separation,and so on [1⁃10].Although a variety of metal CPs with desired
structures and functions have been synthesized to date,rational control in the construction of polymers remains a great challenge in crystal engineering.In order to pre⁃
pare CPs with desired structures and functionalities,
judicious selection of appropriate polydentate organic ligands and metal ions could be the key factors of effec⁃tive and facile approach
[11⁃14]
.So many multidentate
ligand contain multi⁃oxygen,nitrogen and halogen
atoms donor are often employed as bridging ligands to construct CPs,due to their extension ability both in
covalent bonding and in supramolecular interactions (H ⁃bonding and aromatic stacking)[15⁃18].
4⁃(2,4,6⁃tricarboxylphenyl)⁃2,2′,6′,2″⁃terpyridine
(H 3tbtd)and 1⁃fluoro⁃2,4,6⁃phenyltriacid (H 3bbta)are
such typical example of multidentate N,O and F donor
ligand,having three carboxyl groups and one terpyridyl
group/fluorine atom attached to the benzene rings.So,they have nine/seven potential donor atoms,which allows the formation of variable structures with differ⁃ent topologies and dimensions constructed from differ⁃ent directions.Furthermore,they have three carboxyl groups that may be completely or partially deprotonat⁃ed,and can provide hydrogen bond donors and accep⁃tors,which make them a wonderful candidate for the construction of supramolecular networks depending upon the number of deprotonated carboxylate groups.Therefore,they may be an excellent candidate for the construction of multidimensional coordination poly⁃mers.However,to the best of our knowledge,tbtd⁃metal CP and bbta⁃metal CP have rarely been reported [19].With the aim of understanding the coordination
chemistry of H 3tbtd and H 3bbta and studying their
properties,we have recently engaged in the research of
this kind of CPs.Luckily,we have now obtained one
CP,{[Co 3(tbtd)2(bpy)2(H 2O)]·5H 2O}n (1),and one com⁃plex,[Cd 2(Hbbta)(bpy)3(C 2O 4)(H 2O)](2).Herein we
described their syntheses,structures,luminescence,thermal stabilities and photocatalytic
behaviors.Scheme 1Coordination modes of tbtd 3-(a)and Hbbta 2-(b)ligand in 1~2
1
Experimental
1.1
Reagents and physical measurements
All chemicals and reagents were used as received from commercial sources without further purification.All reactions were carried out under hydrothermal con⁃ditions.Elemental analyses (C,H,N)were determined
with a Elementar Vario EL Ⅲelemental analyser.IR spectra were recorded as KBr pellets on a Bruker
EQUINOX55spectrophotometer in the 4000~400cm -1region.Thermogravimetric analyses (TGA)were performed in a nitrogen atmosphere with a heating rate of 10℃·min -1with a NETZSCHSTA 449C thermo⁃gravimetric analyzer.Powder X⁃ray diffraction patterns (PXRD)were recorded with a Rigaku D/Max Ⅲdiffrac⁃tometer operating at 40kV and 30mA using Cu Kαradiation (λ=0.15418nm)at a scanning rate 2(°)·
min -1from 5°to 50°.
陈小莉等：基于三联吡啶/苯三羧酸类配体构筑的两个配合物的合成、结构和性质341
无机化学学报第37卷
Photocatalytic experiments in aqueous solutions
were carried out in typical processes.A suspension containing CP 1(15mg)and 25mL of methylene or⁃
ange (MO)(10mg·L -1)solution was stirred in the dark
for about 30min to ensure the establishment of adsorp⁃
tion equilibrium before irradiation.They were then con⁃ducted on an XPA⁃7type photochemical reactor equipped with a 100W mercury lamp and the reaction temperature was maintained at about 25℃by circulat⁃ing cooling water.Every 15min,a certain volume of samples was collected and separated by centrifugation to remove residual catalyst particles.Then the solution
was analyzed by using Shimadzu UV⁃Vis spectrometer.The concentration of MO was estimated by the absor⁃bance at 463nm,characteristic of MO.1.2
Synthesis of {[Co 3(tbtd)2(bpy)2(H 2O)]·5H 2O}n
(1)
A mixture of Co(Ac)2·4H 2O (24.9mg,0.1mmol),H 3tbtd (44.1mg,0.1mmol),bpy (15.6mg,0.1mmol)
and water (10mL)was stirred and adjusted to pH=6.5
with 0.5mol·L -1NaOH solution,then sealed in a 25mL Telfon ⁃lined stainless steel container,which was
heated to 140℃for 72h.Then the mixture was cooled to room temperature at a rate of 5℃·h -1.Red crystals were obtained in ca.57%yield based on Co.Anal.Calcd.for C 68H 52Co 3N 10O 18(%):C,55.41;H,3.56;N,9.50;Found(%):C,55.46;H,3.52;N,9.45.FT ⁃IR (KBr,cm -1)for 1:3405(s),2995(w),1603(s),1581(s),
1480(m),1349(s),1268(w),1070(w),922(w),811
(m),696(w).
1.3Synthesis of [Cd 2(Hbbta)(bpy)3(C 2O 4)(H 2O)](2)
A mixture of CdCO 3(17.2mg,0.1mmol),H 3bbta (28.8mg,0.1mmol),bpy (15.6mg,0.1mmol)and
water (10mL)was stirred and adjusted to pH=6.0with
0.5mol·L -1Na 2C 2O 4solution,then sealed in a 25mL Telfon⁃lined stainless steel container,which was heat⁃
ed to 160℃for 96h.Then the mixture was cooled to room temperature at a rate of 5℃·h -1.White crystals
were obtained in ca.53%yield based on Cd.Anal.Calcd.for C 41H 28Cd 2FN 6O 11(%):C,48.07;H,2.75;N,
8.20;F,1.85;Found(%):C,48.05;H,2.80;N,8.22;F,1.83.FT⁃IR (KBr,cm -1)for 2:3426(s),3056(w),1703(m),1606(s),1568(s),1437(s),1268(m),1099(w),
1006(w),859(m),761(m),696(m).1.4
X⁃ray crystallography
Intensity data were collected on a Bruker Smart
APEX ⅡCCD diffractometer with graphite⁃monochro⁃mated Mo Kαradiation (λ=0.071073nm)at room tem⁃
perature.
Empirical
absorption
corrections
were
applied using the SADABS program.The structures
were solved by direct methods and refined by the full⁃matrix least⁃squares based on F 2using SHELXTL⁃
2014/2016program [20].All non ⁃hydrogen atoms were
refined anisotropically and hydrogen atoms of organic
ligands were generated geometrically.Crystal data and
structural refinement parameters for 1~2are summa⁃rized in Table 1.Selected bond distances and bond angles are listed in Table 2,and hydrogen parameters
are listed in Table 3.
Table 1
ac reactorCrystal data and structural refinement parameters for 1~2
Complex
Empirical formula Formula weight Crystal system Space group a /nm b /nm c /nm α/(°)β/(°)γ/(°)V /nm 3Z
1
C 68H 52Co 3N 10O 181473.98Monoclinic P 21/c 2.28821(10)
1.71209(8)
1.75149(7)
110.8450(10)6.4126(5)
42
C 41H 28Cd 2FN 6O 111024.49Triclinic P 1
1.1896(5)
1.3243(5)
1.5255(6)
107.522(6)106.013(6)99.915(6)
2.1157(14)
2
342
第2期D c /(g·cm -3)
θrange for data collection /(°)
Absorption coefficient /mm -1Crystal size /mm F (000)
Reflection collected Limiting⁃indices Goodness⁃of⁃fit (on F 2)
R 1,wR 2a [I >2σ(I )]R 1,wR 2a (all data)
1.5271.71~25.01
0.8500.32×0.19×0.12
2996
11336-26≤h ≤27,-20≤k ≤20,-20≤l ≤12
0.940
0.0555,0.14970.0725,0.1629
1.608
1.494~30.8111.075
0.26×0.21×0.14
1018
10632-13≤h ≤16,-14≤k ≤18,-19≤l ≤18
1.034
0.0345,0.09940.0572,0.1138
Continued Table 1
a
R 1=∑||F o |-|F c ||/∑|F o |,wR 2=[∑w (F o 2-F c 2)2/∑w (F o 2)2]1/2
Table 2
Selected bond distances (nm)and bond angles (°)for 1~2
1
Co1—O3A
Co1—N5Co2—O7B
Co2—N8Co3—N4
Co3—O13O3A —Co1—N6
O3A —Co1—N5O3A —Co1—N7
N5—Co1—N7
O6—Co1—O5
O7B —Co2—N9
O7B —Co2—N8
O7B —Co2—N10
N8—Co2—N10
O9—Co2—O10
N1—Co3—O12
N1—Co3—N3
N1—Co3—N2
N1—Co3—N4
N3—Co3—N42
Cd1—O7
Cd2—O2
Cd1—O3
Cd2—N6O7—Cd1—O5
O1—Cd2—N3
O7—Cd1—N1
O2—Cd2—N4
0.2009(3)
0.2157(4)
0.1974(3)
0.2131(4)
0.2138(4)
0.2087(4)
122.97(13)94.84(14)
101.85(14)152.02(13)58.06(12)121.02(14)95.64(15)
96.06(15)153.19(14)59.08(11)
95.78(15)99.35(17)
77.70(15)
176.05(18)76.87(17)
0.2241(7)
0.2302(3)
0.2341(2)
0.2326(3)
92.35(10)
97.51(10)
103.37(10)
150.60(9)
Co1—N6Co1—N7Co2—N9Co2—N10
Co3—N1Co3—N3O3A —Co1—O6N6—Co1—N5N6—Co1—N7O3A —Co1—O5N5—Co1—O5
O7B —Co2—O9N9—Co2—N8
N9—Co2—N10
O7B —Co2—O10
N8—Co2—O10
N1—Co3—O13
O12—Co3—N3
O12—Co3—N2
O12—Co3—N4
N2—Co3—N4Cd2—O1Cd1—O4Cd2—N5Cd1—N2
O1—Cd2—N4
O7—Cd1—O3
O2—Cd2—O1
O5—Cd1—O3
0.2052(3)
0.2178(4)0.2035(3)
0.2167(4)
0.2083(4)
0.2126(4)89.81(13)
76.36(13)
75.72(13)
146.47(12)90.30(14)
90.819(13)
76.95(13)
76.34(13)
147.25(13)86.24(13)
90.84(16)87.42(14)
170.90(14)83.01(16)
103.07(16)0.2311(2)0.2285(2)
0.2302(3)
0.2371(3)94.44(10)
95.03(10)
71.92(9)
167.89(9)
Co1—O6
Co1—O5
Co2—O9
Co2—O10Co3—O12Co3—N2
N6—Co1—O6
O6—Co1—N5
O6—Co1—N7
N6—Co1—O5
N7—Co1—O5
N9—Co2—O9
O9—Co2—N8
O9—Co2—N10
N9—Co2—O10
N10—Co2—O10
O12—Co3—O13
O13—Co3—N3
O13—Co3—N2
O13—Co3—N4
Cd1—O5
Cd2—N4Cd1—N1Cd2—N3O7—Cd1—O4
O1—Cd2—N6
O7—Cd1—N2
O2—Cd2—N5
0.2064(3)
0.2372(3)
0.2084(3)
0.2297(3)
0.2085(3)
0.2130(4)
145.78(12)
113.49(16)89.09(15)
90.44(12)88.06(13)
146.23(13)
113.50(15)90.37(15)
91.32(11)96.65(13)
92.84(14)
169.76(16)87.39(15)
92.97(17)0.2294(3)
0.2321(3)
0.2292(3)
0.2327(3)
95.36(10)
91.09(10)
170.22(10)88.29(10)
陈小莉等：基于三联吡啶/苯三羧酸类配体构筑的两个配合物的合成、结构和性质
343
无机化学学报第37卷
CCDC:1986403,1;2004223,2.2Results and discussion
2.1
Structure description of 1
The asymmetric unit of 1contains three indepen⁃
dent Co ions,two tbtd 3-ligands,two coordinated bpy ligands,one coordinated water molecule and five lat⁃
tice water molecules.As shown in Fig.1,Co1is sur⁃
rounded by three nitrogen atoms (N5,N6and N7)from
one chelating tbtd
3-
ligand (Co1—N50.2157(4)nm,
Co1—N60.2052(3)nm,Co1—N70.2178(4)nm),three oxygen atoms (O3A,O5and O6)from two carbox⁃ylate groups of two tbtd 3-ligand.The coordination geometry of Co1center can be described as a distorted octahedral geometry.Similar to Co1,Co2lies in a gen⁃eral position and coordinates to three oxygen atoms
from two carboxylate groups of two tbtd 3-ligands,three nitrogen atoms from a chelating tbtd 3-ligand.The bond lengths of Co2—N are comparable to the reported ones [21],varying from 0.2035(3)to 0.2167(4)nm.
The Co2—O distances fall in a range of 0.1974(3)~
0.2297(3)nm.Whereas Co3center is ligated by four nitrogen atoms from two chelating bpy ligands (Co3—
N10.2083(4)nm,Co3—N20.2130(4)nm,Co3—N3
0.2126(4)nm,Co3—N40.2138(4)nm),one bridging oxygen atom from carboxylate group of a tbtd 3-ligand and one oxygen atom (O13A)from an aqua ligand to
complete a distorted octahedral geometry.The Co3—O
distances fall in a range of 0.2083(3)~0.2087(3)nm,
similar to those found in other Co⁃MOFs [22].
It noteworthy that the completely deprotonated tbtd 3-ligand adopts a septadentate chelating and bridg⁃ing coordination mode (Scheme 1a).Two carboxylate groups coordinate with two Co  ions monodentately.One carboxylate group chelate with one Co  ions
bidentately.On the other hand,three nitrogen atoms on terpyridine ring coordinates with a Co ion by triden⁃tately.In order to adapt to the formation of coordination bond,the terpyridine ring and benzene ring of tbtd 3-
ligand are distorted.The dihedral angle of the terpyri⁃Continued Table 2
O5—Cd1—N2
O2—Cd2—N6
O4—Cd1—N1
N5—Cd2—O1
N1—Cd1—O5
N5—Cd2—N6
80.75(10)
108.69(11)
154.65(9)
148.44(10)98.09(10)
71.83(11)O2—Cd2—N3
O4—Cd1—O3
N4—Cd2—N6
O3—Cd1—N2
N5—Cd2—N3
N1—Cd1—N2
84.57(11)
71.73(8)
97.21(11)
92.97(10)
104.98(11)71.04(9)
O4—Cd1—O5
N4—Cd2—N3
O4—Cd1—N2
N5—Cd2—N4
N1—Cd1—O3
N3—Cd2—N6
98.06(10)
71.22(11)
92.49(10)
113.49(10)89.53(9)
166.00(11)Symmetry codes:A:-x -1,y +1/2,-z -1/2;B:-x ,y -1/2,-z +1/2for 1.
Table 3
Hydrogen bond parameters for 1and 2
D —H...A 1O14D —H14a (3)
O14D —H14b (15)
O15D —H15a (14)
O15D —H15b (16)
O17G —O9C 2O5A —H5a (4)
C1A —H1a (9)
C19D —H19a (3)
C18E —H18a (8)
d (D —H)/nm 0.0848(2)
0.0856(3)
0.0867(3)
0.0862(3)
0.0850(3)0.0903(3)
0.0930(6)
0.0930(2)
0.0931(7)
d (H…A)/nm 0.20814(2)
0.2054(4)
0.2696(2)
0.2179(3)
0.3220(3)0.1090(5)
0.2674(6)
0.2478(3)
0.2410(6)
d (D…A)/nm 0.2886(3)
0.2895(5)
0.2835(4)
0.2949(3)
0.3004(3)0.2757(3)
0.3258(8)
0.3216(6)
0.3188(6)
∠DHA /(°)158.81(3)
166.84(3)
101.80(3)
148.66(3)97.01(3)
157.78(7)
121.43(6)
136.47(8)
141.04(9)
Symmetry codes:C:1+x ,2.5-y ,0.5+z ,D:-x ,2-y ,-z ;E:-x ,1-y ,-z ;F:1+x ,2+y ,1+z ;G:1-x ,1.5+y ,0.5-z ;H:1+x ,1+y ,1+z for
1;A:x ,y ,-1+z ;B:-x ,-y ,-1-z ;C:1-x ,1-y ,1-z ,D:x ,1+y ,z ;E:x ,1+y ,z for 2.
344

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