New complexes constructed from: In situ nitration of (1 H -tetrazol-5-yl)phenol: Synthesis, structures and properties

Article abstract of DOI:10.1039/c7ce00753a

Nine new complexes, {[Zn₃(L¹)₂(OH)₂]·H₂O}_n (1), [Ag₂(L¹)]_n (2), {[Co(HL¹)₂(H₂O)₄]·2H₂O} (3), [Cu₃(L¹)₂(OH)₂(H₂O)]_n (4), {[Cu₇(HL¹)₂(L¹)₆(H₂O)₆]·11.1H₂O}_n (5), {[Cu(L¹)(H₂O)₃]·8H₂O}_n (6), [Ag₂(L²)]_n (7), [Ag₈(L³)₄(H₂O)]_n (8) and [Cu(L³)(H₂O)₂]_n (9) [H₂L¹ = 2,6-dinitro-4-(1H-tetrazol-5-yl)phenol, H₂L² = 2,4,6-trinitro-3-(1H-tetrazol-5-yl)phenol, H₂L³ = 2,4-dinitro-6-(1H-tetrazol-5-yl)phenol], have been solvothermally synthesized via in situ nitration from 4-(1H-tetrazol-5-yl)phenol, 3-(1H-tetrazol-5-yl)phenol and 2-(1H-tetrazol-5-yl)phenol precursors as well as nitrate salts as nitration reagents and structurally characterized by single-crystal X-ray diffraction, infrared spectroscopy (IR), elemental analysis, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The structures of the complexes vary from 3D frameworks for 1, 4 and 7, 2D networks for 2, 5 and 8, 1D chains for 6 and 9, to a discrete 0D structure for 3, showing 2D supramolecular structures by interlayer π-π stacking. Topological classification of 2D and 3D architectures was performed, disclosing a variety of topological symbols: (4²·6)₂(4⁴·6²·8⁸·10) for 1, (4³)₂(4⁶·6⁶·8³) for 2, (4⁶)₂(4¹²·61²·8⁴) for 4, (6³) for 5 and (4⁵·6)(4⁷·6³)(4¹⁸·6¹⁶·8²) for 7. The contrast of 1-9 reveals that ligands and metal salts have important influences on adjusting the crystal structures; notably, the coordination modes of the ligands can also tune the structures of 4-6 which possess the same ligands and nitration agents. The solid-state UV-vis spectra and band gap energy of the nine complexes were investigated. In addition, the luminescence properties (for complexes 1-3, 7 and 8) and magnetic properties (for complexes 3-6 and 9) were also discussed.

Full text of DOI:10.1039/c7ce00753a

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New complexes constructed from in situ nitration
of (1H-tetrazol-5-yl)phenol: synthesis, structures
and properties†
Cite this: DOI: 10.1039/c7ce00753a
Ceng-Ceng Du,a Xin-Fang Wang,a Sheng-Bin Zhou,a
ab
and Dianzeng Jiab
*
Duo-Zhi Wang
Nine new complexes, {[Zn3IJL1)2IJOH)2]·H2O}n (1), [Ag2IJL1)]n (2), {[CoIJHL1)2IJH2O)4]·2H2O} (3),
[Cu3IJL1)2IJOH)2IJH2O)]n (4), {[Cu7IJHL1)2IJL1)6IJH2O)6]·11.1H2O}n (5), {[CuIJL1)IJH2O)3]·8H2O}n (6), [Ag2IJL2)]n (7),
[Ag8IJL3)4IJH2O)]n (8) and [CuIJL3)IJH2O)2]n (9) [H2L1 = 2,6-dinitro-4-(1H-tetrazol-5-yl)phenol, H2L2 = 2,4,6-
trinitro-3-(1H-tetrazol-5-yl)phenol, H2L3
=
2,4-dinitro-6-(1H-tetrazol-5-yl)phenol],
have been
solvothermally synthesized via in situ nitration from 4-(1H-tetrazol-5-yl)phenol, 3-(1H-tetrazol-5-yl)phenol
and 2-(1H-tetrazol-5-yl)phenol precursors as well as nitrate salts as nitration reagents and structurally char-
acterized by single-crystal X-ray diffraction, infrared spectroscopy (IR), elemental analysis, powder X-ray
diffraction (PXRD) and thermogravimetric analysis (TGA). The structures of the complexes vary from 3D
frameworks for 1, 4 and 7, 2D networks for 2, 5 and 8, 1D chains for 6 and 9, to a discrete 0D structure for
3, showing 2D supramolecular structures by interlayer π–π stacking. Topological classification of 2D and 3D
architectures was performed, disclosing a variety of topological symbols: (42·6)2IJ44·62·88·10) for 1, (43)2IJ46
·66·83) for 2, (46)2IJ412·612·84) for 4, (63) for 5 and (45·6)IJ47·63)IJ418·616·82) for 7. The contrast of 1–9 reveals
that ligands and metal salts have important influences on adjusting the crystal structures; notably, the coor-
dination modes of the ligands can also tune the structures of 4–6 which possess the same ligands and ni-
tration agents. The solid-state UV-vis spectra and band gap energy of the nine complexes were investi-
gated. In addition, the luminescence properties (for complexes 1–3, 7 and 8) and magnetic properties (for
complexes 3–6 and 9) were also discussed.
Received 20th April 2017,
Accepted 23rd October 2017
DOI: 10.1039/c7ce00753a
rsc.li/crystengcomm
target products that exhibit intriguing structures and promis-
ing properties from in situ solvothermal reactions being not a
Introduction
Investigation of coordination polymers (CPs) has evoked par-
ticular interest not only due to their intriguing structural ar-
chitectures and topologies but also because of their wide ap-
plications as functional materials in the fields of
luminescence,1 magnetism,2 catalysis,3 gas storage,4 and so
forth. The design and assembly of functional materials are
still an essential scientific challenge due to different influence
factors5 and synthesis methods. Many novel CPs can be
obtained via in situ ligand reactions, which are inaccessible in
normal direct preparation.6 The in situ solvothermal reaction
can open up new avenues in the field of assembly of multitu-
dinous CPs, despite the exertion of synthetic control over our
trivial task on account of unexpected ligands.7 To date, a vari-
ety of types of in situ reactions, such as hydroxylation,8 alkyl-
ation,9 acylation,10 decarboxylation,11 hydrolysis,12 tetrazole13
and triazole formation,14 and so on, have been observed.
Among these reactions, the electrophilic nitration of arenes
introducing nitrogen atoms into aromatic rings has long been
the classical synthetic approach for the preparation of aro-
matic nitro compounds which are important intermediates
and versatile building blocks15 in the fields of organic synthe-
sis and pharmaceutical science as well as the chemical indus-
try. Generally, concentrated nitric acid and concentrated sul-
furic acid, a type of nitrating agent, are widely used in
nitration reactions.16 The use of such corrosive reagents (es-
pecially in excess) creates serious environmental issues and
the treatment and disposal of the used mixed acids are expen-
sive and difficult; thus, the choice of environmentally friendly
nitration reagents such as nitrate salts is very necessary.17
Some literature studies have reported that ligands containing
aromatic rings and nitrate salts as nitration reagents were
used to construct metal complexes via in situ nitration.18
a Key Laboratory of Energy Materials Chemistry, Ministry of Education, Institute
of Applied Chemistry, Xinjiang University, Urumqi, 830046 Xinjiang, P. R. China.
E-mail: wangdz@xju.edu.cn
b College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi
830046, P. R. China
† Electronic supplementary information (ESI) available. CCDC 1539476–1539484.
For ESI and crystallographic data in CIF or other electronic format see DOI:
10.1039/c7ce00753a
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However, there have been no reports on CPs synthesized
through in situ nitration from the phenol ligand containing a
tetrazole moiety, as a tether or a molecular tecton, which pos-
sesses four nitrogen atoms with versatile binding modes and
has been extensively utilized in the formation of diverse
frameworks with exciting functional properties,19 among
which 5-substituted-1H-tetrazole is the most important and
popular species used to construct novel architectures.20
samples were accomplished over the 2θ range of 5–60° on a
Rigaku D/Max-2500 diffractometer at 40 kV and 100 mA with
a
Cu-target tube and
a
graphite monochromator.
Thermogravimetric analysis (TGA) data were determined
using a Perkin-Elmer TG-7 thermal analyzer from 25 °C to
800 °C at a rate of 10 °C min−1 under an Ar atmosphere. UV-
vis absorption spectra were acquired on a Hitachi UV-3010
UV-vis spectrophotometer. Solid-state luminescence spectra
were detected on a Hitachi F-4500 fluorescence spectropho-
tometer with a Xe arc lamp as the light source and band-
widths of 2.5 nm at room temperature. Fluorescence lifetime
data were obtained on a Fluorolog-3 spectrofluorometer.
Magnetic measurements of the samples were performed on a
SQUID MPMS-XL-7 magnetometer (Scheme 2).
Taking into consideration the above background informa-
tion, three phenol precursors were selected in this work,
4-(1H-tetrazol-5-yl)phenol, 3-(1H-tetrazol-5-yl)phenol and 2-(1H-
tetrazol-5-yl)phenol, substituted by the tetrazole rings at dif-
ferent positions, as well as nitrate salts to induce in situ nitra-
tion and to construct nine new complexes, namely,
{[Zn3IJL1)2IJOH)2]·H2O}n (1), [Ag2IJL1)]n (2), {[CoIJHL1)2IJH2O)4]
·2H2O} (3), [Cu3IJL1)2IJOH)2IJH2O)]n (4), {[Cu7IJHL1)2IJL1)6IJH2O)6]
·11.1H2O}n (5), {[CuIJL1)IJH2O)3]·8H2O}n (6), [Ag2IJL2)]n (7),
[Ag8IJL3)4IJH2O)]n (8) and [CuIJL3)IJH2O)2]n (9) [H2L1 = 2,6-dinitro-
4-(1H-tetrazol-5-yl)phenol, H2L2 = 2,4,6-trinitro-3-(1H-tetrazol-5-
Synthesis of complexes 1–9
{[Zn3IJL1)2IJOH)2]·H2O}n (1). A mixture of ZnIJNO3)2·6H2O
(89.3 mg, 0.30 mmol) and 4-(1H-tetrazol-5-yl)phenol (24.3 mg,
0.15 mmol) in the component solvent (H2O/CH3CH2OH = 1 :
1, 8 mL) was sealed in a 25 mL Teflon-lined stainless steel
vessel and heated to 140 °C for 24 hours, then slowly cooled
to room temperature at a rate of 5 °C h−1. Yellow block crys-
tals of 1 were isolated in a 61% yield based on L1. Anal. calcd
(%) for C14H8N12O13Zn3: C, 22.47; H, 1.08; N, 22.46. Found:
C, 22.62; H, 1.27; N, 22.18. IR (cm−1, KBr pellets): 3545(m),
3090(w), 1793(w), 1634(s), 1557(s), 1492(s), 1452(m), 1413(m),
1378(m), 1350(m), 1329(m), 1247(s), 1177(w), 1144(m), 1077(w),
1051(w), 899(w), 841(m), 781(w), 768(w), 708(w), 650(w), 605(w),
585(w) (Fig. S2 of the ESI†).
yl)phenol, H2L3
=
2,4-dinitro-6-(1H-tetrazol-5-yl)phenol]
(Scheme 1), giving different dimensionalities from 0D to 3D,
characterized by single-crystal X-ray diffraction, infrared
spectroscopy (IR), elemental analysis, powder X-ray diffrac-
tion (PXRD) and thermogravimetric analysis (TGA). The ef-
fects of different positions of the tetrazole substituent on the
nitration reaction were studied. In addition, the solid-state
UV-vis spectra and band gap energy of the nine complexes
were investigated, and the luminescence properties (for com-
plexes 1–3, 7 and 8) and magnetic properties (for complexes
3–6 and 9) were also discussed.
[Ag2IJL1)]n (2). A mixture of AgNO3 (17.0 mg, 0.10 mmol),
4-(1H-tetrazol-5-yl)phenol (16.2 mg, 0.1 mmol) and H2O (8
mL) was sealed in a 25 mL Teflon-lined stainless steel vessel
and heated to 140 °C for 48 hours, then slowly cooled to
room temperature at a rate of 5 °C h−1. Yellow block crystals
of 2 were isolated in a 42% yield based on Ag. Anal. calcd (%)
for C7H2N6O5Ag2: C, 18.05; H, 0.43; N, 18.04. Found: C, 18.37;
H, 0.29; N, 18.31. IR (cm−1, KBr pellets): 3061(w), 2921(w),
1854(w), 1632(m), 1551(s), 1516(m), 1481(s), 1435(m),
1418(w), 1366(w), 1324(s), 1254(s), 1159(w), 1135(w), 1106(w),
1069(w), 1045(w), 919(w), 909(m), 824(w), 787(w), 765(m),
716(m), 638(w), 587(w) (Fig. S2 of the ESI†).
Experimental section
Materials and general methods
All of the commercially available chemicals in the reactions
were used as received without further purification. The 4-(1H-
tetrazol-5-yl)phenol, 3-(1H-tetrazol-5-yl)phenol and 2-(1H-
tetrazol-5-yl)phenol precursors were synthesized with the cor-
responding nitriles and NaN3 according to the reported litera-
ture.21 1H NMR spectra for 4-(1H-tetrazol-5-yl)phenol, 3-(1H-
tetrazol-5-yl)phenol and 2-(1H-tetrazol-5-yl)phenol precursors
are depicted in Fig. S1 of the ESI.† Elemental analyses of C,
N, and H were conducted on a Thermo Flash EA 1112-NCHS-
O analyzer. IR spectra using KBr pellets were recorded on a
Bruker Equinox 55 FT-IR spectrometer in the range of 4000–
400 cm−1. Powder X-ray diffraction (PXRD) analyses of bulk
{[CoIJHL1)2IJH2O)4]·2H2O} (3). A mixture of CoIJNO3)2·6H2O
(29.1 mg, 0.1 mmol), 4-(1H-tetrazol-5-yl)phenol (32.4 mg, 0.20
mmol) and a drop of concentrated hydrochloric acid in H2O
(8 mL) was placed in a Teflon-lined autoclave and heated to
Scheme 1 The ligands involved in this work.
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Scheme 2 Synthetic routes to complexes 1–9.
140 °C for 24 hours, then slowly cooled to room temperature
at a rate of 5 °C h−1. Pink block crystals of 3 were isolated in
a 63% yield based on Co. Anal. calcd (%) for C14H18N12O16Co:
C, 25.12; H, 2.71; N, 25.11. Found: C, 25.20; H, 2.68; N, 25.22.
IR (cm−1, KBr pellets): 3573(s), 3546(s), 3339(s), 3204(s),
2807(m), 2585(w), 2510(w), 2449(w), 2232(w), 2017(w),
1881(w), 1857(w), 1826(w), 1639(s), 1577(s), 1545(s), 1525(s),
1472(s), 1412(m), 1378(m), 1337(s), 1256(s), 1172(s), 1099(s),
1043(m), 944(w), 913(s), 892(m), 813(m), 786(m), 733(m),
708(s), 683(s), 594(s) (Fig. S2 of the ESI†).
721(m). For 6: Anal. calcd (%) for C7H24N6O16Cu: C, 16.42; H,
4.73; N, 16.42. Found: C, 16.55; H, 4.45; N, 16.35. IR (cm−1
,
KBr pellets): 3531(m), 3078(m), 2355(w), 2026(w), 1873(w),
1625(s), 1545(s), 1522(s), 1485(s), 1446(s), 1423(s), 1329(s),
1234(s), 1107(m), 1072(m), 1041(m), 929(m), 842(m), 789(m),
761(m), 715(m), 675(m), 638(m) (Fig. S2 of the ESI†).
[Ag2IJL2)]n (7). A mixture of AgNO3 (17.0 mg, 0.10 mmol),
3-(1H-tetrazol-5-yl)phenol (32.4 mg, 0.20 mmol) and a drop of
concentrated hydrochloric acid in H2O (8 mL) was placed in
a Teflon-lined autoclave and heated to 180 °C for 48 hours,
then slowly cooled to room temperature at a rate of 5 °C h−1.
Yellow strip crystals of 7 were isolated in a 61% yield based
on Ag. Anal. calcd (%) for C7HN7O7Ag2: C, 16.46; H, 0.20; N,
19.19. Found: C, 16.28; H, 0.37; N, 19.34. IR (cm−1, KBr pel-
lets): 3447(w), 3086(w), 2904(w), 1611(s), 1537(s), 1502(s),
1326(s), 1285(s), 1247(s), 1159(m), 1045(m), 963(m), 926(m),
871(m), 784(m), 743(w), 711(m), 616(w), 565(w), 467(w) (Fig.
S2 of the ESI†).
[Cu3IJL1)2IJOH)2IJH2O)]n (4). The preparation of 4 was simi-
lar to that of 2 except that CuIJNO3)2·3H2O (24.2 mg, 0.10
mmol) was used instead of AgNO3 (17.0 mg, 0.10 mmol).
Green block crystals of 4 were isolated in a 35% yield based
on Cu. Anal. calcd (%) for C14H12N12O13Cu3: C, 22.51; H, 1.61;
N, 22.50. Found: C, 22.45; H, 1.55; N, 22.48. IR (cm−1, KBr
pellets): 3633(w), 3573(m), 3529(s), 3074(w), 3038(w), 2819(w),
2518(w), 2242(w), 1860(w), 1634(s), 1561(s), 1529(s), 1496(s),
1459(m), 1407(m), 1358(s), 1341(s), 1312(m), 1266(s),
1194(w), 1168(w), 1132(w), 1112(m), 1093(m), 1075(m),
1037(m), 920(s), 833(w), 789(w), 775(m), 758(w), 733(m),
718(m), 700(w), 631(m), 608(w) (Fig. S2 of the ESI†).
[Ag8IJL3)4IJH2O)]n (8). The preparation of 8 was similar to
that of 7 except that 2-(1H-tetrazol-5-yl)phenol (32.4 mg, 0.20
mmol) was used instead of 3-(1H-tetrazol-5-yl)phenol (32.4
mg, 0.20 mmol). Yellow strip crystals of 8 were isolated in a
58% yield based on Ag. Anal. calcd (%) for C28H10N24O21Ag8:
C, 17.87; H, 0.54; N, 17.87. Found: C, 17.69; H, 0.39; N, 17.67.
IR (cm−1, KBr pellets): 3567(w), 3106(w), 3054(w), 2884(w),
2480(w), 1829(w), 1601(s), 1555(m), 1525(s), 1454(m),
1415(m), 1376(m), 1333(s), 1296(s), 1259(s), 1167(m),
1149(m), 1095(m), 1049(m), 937(w), 922(w), 833(w), 794(w),
736(w), 705(m) (Fig. S2 of the ESI†).
{[Cu7IJHL1)2IJL1)6IJH2O)6]·11.1H2O}n (5) and {[CuIJL1)IJH2O)3]
·8H2O}n (6). The preparation of 5 was similar to that of 3 ex-
cept that CuIJNO3)2·3H2O (24.2 mg, 0.10 mmol) was used in-
stead of CoIJNO3)2·6H2O (87.3 mg, 0.3 mmol). Brown strip
crystals of 5 were isolated in a 41% yield based on Cu. The
filtrate was allowed to stand at room temperature after sev-
eral days. Green block crystals of 6 were isolated in a 28%
yield based on Cu. For 5: Anal. calcd (%) for
C56H52.2N48O57.1Cu7: C, 24.41; H, 1.91; N, 24.40. Found: C,
24.58; H, 1.29; N, 24.03. IR (cm−1, KBr pellets): 3513(m),
3371(m), 3088(w), 1847(w), 1626(s), 1538(s), 1499(s), 1425(s),
1339(s), 1299(m), 1251(s), 1152(m), 1106(m), 1082(m),
1033(m), 938(w), 915(m), 829(w), 789(w), 778(w), 754(m),
[CuIJL3)IJH2O)2]n (9). 9 was synthesized by the same proce-
dure as that for 5 using 2-(1H-tetrazol-5-yl)phenol (32.4 mg,
0.20 mmol) instead of 4-(1H-tetrazol-5-yl)phenol (32.4 mg,
0.20 mmol). Green block crystals of 9 were isolated in a 48%
yield based on Cu. Anal. calcd (%) for C7H6N6O7Cu: C, 24.04;
H, 1.73; N, 24.03. Found: C, 24.32; H, 1.58; N, 24.32. IR
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(cm−1, KBr pellets): 3521(w), 3078(w), 1606(s), 1573(s),
1531(s), 1495(s), 1478(s), 1383(w), 1343(s), 1316(s), 1283(s),
1201(m), 1173(m), 1104(m), 1066(w), 988(w), 933(w), 843(w),
793(w), 745(m), 709(m), 544(w), 457(w) (Fig. S2 of the ESI†).
Caution! These complexes may be explosive, so they must be
handled carefully.
O4#4) from one L1 ligand and one oxygen atom (O1) from one
μ2-OH− anion to generate a distorted [ZnN2O3] square pyrami-
dal coordination sphere with N2, O1, O3#4 and O4#4 in the
equatorial plane and N4#1 at the axial position in Fig. 1a. The
Zn–N bond lengths vary in the range of 2.029IJ2)–2.107IJ2) Å,
and the Zn–O bond lengths vary from 1.9002(19) to 2.409(2)
Å, respectively. It is interesting to note that all L1 ligands with
the dihedral angle between the tetrazole ring and the ben-
zene ring being 64.48° (Fig. S3a of the ESI†) display a μ4-κO3,
O4:κN1:κN2:κN4 coordination mode (mode A in Scheme 3) to
link one Zn1 and three Zn2. One Zn1 and one Zn2 are doubly
bridged by one μ2-OH− anion and one tetrazole ring and,
through such bridges, one Zn1 is linked to two Zn2 to form a
X-ray crystallography
The single-crystal X-ray diffraction measurements of 1–9 were
fulfilled using a Bruker Smart Apex-II CCD diffractometer,
which was equipped with a normal focus, sealed tube X-ray
source with graphite-monochromated Mo-Kα radiation (λ =
0.71073 Å) using both φ- and ω-scan modes at room tempera-
ture. The data for 1–9 were applied for empirical absorption
correction with the SADABS program22 and data reduction
was performed using SAINT software.23 The crystal structures
were solved by direct methods and refined on F2 by the full-
matrix least-squares technique using the SHELXL-2014 pro-
gram.24 All non-hydrogen atoms were refined anisotropically.
The hydrogen atoms were located by geometrical calcula-
tions, and their positions and thermal parameters were fixed
during the structure refinement, where it was found that
there are disordered groups or atoms in some structures. The
highly disordered guest molecules of complexes 3, 5 and 6
are difficult to model, therefore, the contributions of disor-
dered solvent were removed by the SQUEEZE25 program in
PLATON for complexes 3, 5 and 6. The 18, 111 and 23
electrons of complexes 3, 5 and 6 removed from the unit cell
by the squeeze process could correspond to 1.8, 11.1 and 1.15
water molecules, respectively. The value of the Flack parame-
ter for complex 7 is [0.5(2)]. The crystallographic data for 1–9
are summarized in Table 1, and selected bond lengths and
angles are given in Table S1 of the ESI.†
trinuclear metallic cluster of [Zn3IJOH)2IJN4C)2] with
a
Zn1⋯Zn2 separation of 3.3370(3) Å. The trinuclear subunits
are connected to each other through nitrogen atoms of the
tetrazole rings coordinated with Zn2 to generate an infinite
one-dimensional (1D) chain in Fig. 1b. The adjacent chains
associate with each other resulting in a complicated 2D net-
work structure, further forming an extended 3D framework
structure in Fig. 1c. To afford a better insight into the struc-
ture, the trinuclear clusters can be clarified as 6-connected
nodes, and the ligands can be identified as 3-connected
nodes. Accordingly, the whole structure of complex 1 is re-
lated to a binodal (3,6)-connected net with a point symbol of
(42·6)2IJ44·62·88·10).
[Ag2IJL1)]n (2). Complex 2 is solved in the monoclinic C2/c
crystal system. The asymmetric unit of 2 contains one AgIJI)
ion and half of a deprotonated L1 ligand. As illustrated in
Fig. 2a, each AgIJI) ion is four-coordinated by two nitrogen
atoms (N2, N3#1) from two different L1 ligands and two oxy-
gen atoms (O1, O3) from another crystallographically inde-
pendent L1 ligand to furnish a distorted [AgN2O2] tetrahedral
geometry, and the L1 ligand lies about a twofold axis. The
Ag–N bond lengths are 2.322(7) Å and 2.218(7) Å, and the
Ag–O bond lengths are 2.321(5) Å and 2.532(8) Å, respectively.
All bond distances are within the normal range. In complex
2, the L1 ligand showing a dihedral angle of 44.29° for two ar-
omatic rings (Fig. S3b of the ESI†) adopts one type of coordi-
nation mode (mode B in Scheme 3), acting as a hexadentate
linker to chelate two AgIJI) ions and bridge four AgIJI) ions. The
tetrazole ring of the L1 ligand as a quadridentate connector
connects four AgIJI) ions to generate a one-dimensional chain,
and these 1D chains are further connected to form a single
2D layer parallel to the ab plane by coordination interactions
of nitro group oxygen atoms and phenolic group oxygen
atoms with AgIJI) ions (Fig. 2b). It is noteworthy that all AgIJI)
ions are completely coplanar. This network contains two
types of cavities, one is a five-membered ring having the
shortest Ag⋯Ag distance of 3.723(3) Å and the other is a six-
membered ring with the closest distance of 3.875(3) Å. Each
AgIJI) ion is surrounded by three L1 ligands, and each L1 li-
gand attaches to six AgIJI) ions. From the topological point of
view, the AgIJI) ions can be defined as 3-connected nodes and
the organic ligands can be regarded as 6-connected nodes.
Thus, the overall structure of complex 2 can be simplified as
CCDC 1539476–1539484 contains the supplementary crys-
tallographic data for complexes {[Zn3IJL1)2IJOH)2]·H2O}n (1),
[Ag2IJL1)]n (2), {[CoIJHL1)2IJH2O)4]·2H2O} (3), [Cu3IJL1)2IJOH)2IJH2-
O)]n (4), {[Cu7IJHL1)2IJL1)6IJH2O)6]·11.1H2O}n (5), {[CuIJL1)IJH2O)3]
·8H2O}n (6), [Ag2IJL2)]n (7), [Ag8IJL3)4IJH2O)]n (8) and
[CuIJL3)IJH2O)2]n (9), respectively.
Results and discussion
Crystal structures
{[Zn3IJL1)2IJOH)2]·H2O}n (1). Crystal structure determination
reveals that complex 1 is a 3D architecture constituted by
trinuclear [Zn3IJOH)2IJN4C)2] clusters and crystallizes in the
monoclinic crystal system with space group C2/c. The asym-
metric unit of 1 is composed of one and a half ZnIJII) ions,
one L1 ligand, one OH− anion and one dissociative water mol-
ecule. As shown in Fig. 1a, the four-coordinated Zn1 ion is li-
gated by two nitrogen atoms (N1, N1#3) from two different li-
gands and two oxygen atoms (O1, O1#3) from two μ2-OH−
anions to form a distorted [ZnN2O2] tetrahedral geometry; in
addition, the Zn1 atom lies on a twofold axis. The five-
coordinated Zn2 ion is ligated by two nitrogen atoms (N2,
N4#1) from two different L1 ligands, two oxygen atoms (O3#4,
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Fig. 1 (a) Coordination environment of ZnIJII) ions in 1, symmetry code: #1 −x + 3/2, y − 1/2, −z + 3/2; #2 x − 1/2, −y + 1/2, z − 1/2; #3 −x + 1, y, −z
+ 3/2; #4 x + 1/2, −y + 1/2, z + 1/2. (b) The infinite 1D chain formed from trinuclear metallic clusters. (c) View of the complicated 3D framework of
1. (d) Schematic representation of the (3,6)-connected topology of (42·6)2IJ44·62·88·10).
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Scheme 3 Twelve coordination modes (A–L) of ligands in this work.
a 2D (3,6)-connected network with a (43)2IJ46·66·83) topology
(O6#4) from one L1 ligand and two nitrogen atoms (N3#3, N6)
from two different L1 ligands. Cu3 adopts a distorted octahe-
dral geometry where the equatorial positions are occupied by
one oxygen atom (O11) from one μ2-OH− anion and three oxy-
gen atoms (O7#5, O8#5, O1#4) from two different L1 ligands,
while the axial positions are occupied by two nitrogen atoms
(N8, N4#6) from two different L1 ligands. The Cu–N bond dis-
tances span from 1.963(11) to 2.148(11) Å, and the observed
Cu–O bond distances are in the range of 1.853IJ9)–2.593IJ14) Å.
It is worth noting that the L1 ligands completely deprotonate
and adopt two distinct modes when coordinated to CuIJII) ions
in complex 4: one is a μ5-κO3,O4:κO1:κN1:κN3:κN4 coordina-
tion mode (mode D in Scheme 3) with two Cu1, one Cu2 and
two Cu3, and two aromatic rings exhibit a dihedral angle of
approximately 83.69° (Fig. S3d of the ESI†); the other is a μ5-
κO7,O8:κO6:κN5:κN6:κN8 coordination mode (mode E in
Scheme 3) with one Cu1, two Cu2 and two Cu3 with a dihedral
angle of 78.94° for two aromatic rings (Fig. S3e of the ESI†).
One Cu1, one Cu2 and one Cu3 are joined together through
two μ2-OH− anions to furnish a [Cu3IJOH)2] trinuclear cluster
with a Cu⋯Cu average distance of 3.334(4) Å. Such trinuclear
clusters are further bridged by pairs of tetrazole rings from the
ligands with different coordination modes into an infinite
one-dimensional (1D) chain showing a 16-membered macro-
cycle (Fig. 4b). The adjacent chains are arranged by N5, N6, N8
and O6 of the ligands with the other coordination mode with
CuIJII) ions to give a 2D layer generated from undulating
beaded chains and the [Cu2IJL1)2] dimers by sharing Cu3 in an
alternating arrangement, which are made up of a pair of the li-
gands and two Cu3 with a Cu3⋯Cu3 distance of 7.5679(9) Å.
The layers further expand to construct a final 3D framework
with the aid of O3 and O4 with Cu1 coordination interactions
as well as O7 and O8 with Cu3 coordination interactions
(Fig. 4c). Topologically, the trinuclear units could be viewed as
eight-connected nodes, and the two kinds of ligands with two
different coordination modes could be respectively considered
as four-connected nodes. Thus, the overall structure of 4 is a
3D (4,4,8)-connected network with the point symbol of
(46)2IJ412·612·84).
(Fig. 2c).
{[CoIJHL1)2IJH2O)4]·1.8H2O} (3). Complex
3 is a two-
dimensional supramolecular framework constructed from
¯
mononuclear structures. Complex 3 crystallizes in the P1
space group of a triclinic crystal system with one CoIJII) ion,
two HL1 ligands, four coordinated water molecules and 1.8
lattice water molecules in the asymmetric unit. Co1 reveals
an octahedral [CoN2O4] environment, filled by two nitrogen
atoms (N3, N3#1) from two different HL1 ligands and four ox-
ygen atoms (O7, O7#1, O8, O8#1) from four distinct coordi-
nated water molecules (Fig. 3a). Four water molecules are
aligned around the CoIJII) ion in the corners of a square, and
two HL1 ligands within the square are arranged very closely
perpendicular. The Co–N distance is 2.138(8) Å, while the
lengths of Co–O bonds are 2.030(8) Å and 2.138(8) Å; these
bonding parameters are within normal values for related co-
balt complexes. The ligand adopts a monodentate coordina-
tion mode to link one CoIJII) ion to form a mononuclear struc-
ture (mode C in Scheme 3). The tetrazole ring and the
benzene ring of each HL1 ligand are approximately coplanar
and rotate away with a dihedral angle of 3.82° (Fig. S3c of the
ESI†). In the crystal stack of 3, the 2D layer is extended by
π–π interactions between benzene rings of parallel ligands
with an average centroid–centroid separation of 3.671 Å in
Fig. 3b (Table S2 of the ESI†).
[Cu3IJL1)2IJOH)2IJH2O)]n (4). Complex 4 reveals a 3D frame-
¯
work, crystallizing in the triclinic P1 space group. The asym-
metric unit in complex 4 includes three independent CuIJII)
ions, two L1 ligands, two OH− anions and one coordinated wa-
ter molecule. As illustrated in Fig. 4a, the Cu1 ion has a
distorted octahedral coordination environment with two oxy-
gen atoms (O3#1, O4#1) from one L1 ligand, one oxygen atom
(O12) from one μ2-OH− anion and one oxygen atom (O13) from
one coordinated water molecule in the equatorial plane, and
two nitrogen atoms (N1, N5) from two different L1 ligands at
the axial positions. Cu2 exhibits a distorted trigonal bipyrami-
dal coordination configuration by connecting to two oxygen
atoms (O11#2, O12) from two μ2-OH− anions, one oxygen atom
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Fig. 2 (a) Coordination environment of the AgIJI) ion in 2, symmetry code: #1 −x + 3/2, −y + 3/2, −z + 1; #2 x, y − 1, z. (b) The view of the 2D
network constituted by AgIJI) ions and the ligands. (c) Schematic representation of the (3,6)-connected topology of (43)2IJ46·66·83).
{[Cu7IJHL1)2IJL1)6IJH2O)6]·11.1H2O}n (5). Complex 5 is a 2D
slightly distorted square pyramidal environment ([CuN4O] for
Cu1 and [CuN3O2] for Cu3, respectively). Cu1 is coordinated
by four nitrogen atoms (N5, N8, N14#1, N15) from four li-
gands and one oxygen atom (O7) from one μ3-H2O molecule,
while Cu3 is coordinated by three nitrogen atoms (N9, N16,
N20) from three ligands, one oxygen atom (O7) from one μ3-
H2O molecule and another oxygen atom (O8) from one termi-
nal coordinated water molecule. Cu2 is six-coordinated in an
octahedral environment by nitrogen atoms (N4, N21) from
¯
framework and crystallizes in the triclinic space group P1.
The asymmetric unit consists of three and a half CuIJII) ions,
three L1 ligands, one HL1 ligand, three coordinated water
molecules and 5.55 lattice water molecules. The three and a
half CuIJII) ions include Cu1, Cu2, Cu3 and Cu4 (occupancy
rates of 1, 1, 1, and 0.5) showing distorted square pyramidal,
octahedral, square pyramidal and planar coordination geom-
etries, separately. Cu1 and Cu3 are five-coordinated with a
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Fig. 3 (a) Coordination environment of the CoIJII) ion in 3, symmetry code: #1 −x + 1, −y + 1, −z + 2. (b) View of the two-dimensional layer formed
by π–π interactions.
two different ligands, two oxygen atoms (O16#2, O17) from
one ligand, one oxygen atom (O7) from one μ3-H2O molecule
and one oxygen atom (O6) from a terminal coordinated water
molecule. Cu4 is surrounded by four oxygen atoms (O10,
O11, O10#3, O11#3) from two individual ligands with the O10
and O11 atoms as well as the O10#3 and O11#3 atoms in a
chelating fashion, generating a planar coordination sphere in
Fig. 5a. All Cu–N bond lengths fall in the range of 1.942IJ13)–
2.297IJ18) Å, and the Cu–O bond lengths vary from 1.848(14)
to 2.33(2) Å, both falling in normal ranges. The ligands adopt
three different coordination modes: the first type acts as a
bidentate connector to link one Cu1 and one Cu2 with a μ2-
κN4:κN5 coordination mode (mode F in Scheme 3) or to link
one Cu2 and one Cu3 with a μ2-κN20:κN21 coordination
mode (mode F in Scheme 3). Although the coordination
modes are the same, the dihedral angles of two aromatic
rings are 14.09° and 12.76°, respectively (Fig. S3f and S3g of
the ESI†). The second type adopts a μ3-κO10,O11:κN8:κN8 co-
ordination mode (mode G in Scheme 3) connecting one Cu1,
one Cu3 and one Cu4 with a dihedral angle of 6.11° (Fig. S3h
one Cu3, as well as the bond angles of CuIJ1)–OIJ7)–CuIJ2),
CuIJ1)–OIJ7)–CuIJ3) and CuIJ2)–OIJ7)–CuIJ3) being 117.2IJ5)°,
106.3IJ5)° and 113.9IJ4)°, respectively. The trinuclear clusters in
5 are connected with the adjacent ones by N14 and Cu1 coor-
dination interactions and O16, O17 and Cu2 coordination in-
teractions to form a wave-shaped zigzag chain along the a
axis (Fig. 5b). As shown in Fig. 5c, the ligands connect CuIJII)
ions to form a complicated 2D network, which is an assembly
of the trinuclear clusters and Cu4. When the trinuclear clus-
ters are assigned as 3-connected nodes and Cu4 are consid-
ered as 2-connected nodes, the ligands are simplified as
links, and the whole skeleton of 5 can be described as a
3-connected net with the point symbol of (63) in Fig. 5d.
{[CuIJL1)IJH2O)3]·8H2O}n (6). Complex 6 is a 1D chain
¯
which crystallizes in the triclinic P1 space group. The asym-
metric unit of 6 contains one CuIJII) ion, one L1 ligand, three
coordinated water molecules and 1.15 lattice water mole-
cules. Cu1 and Cu2 both with 0.5 occupancy show a
distorted octahedral geometry with the same [CuN2O4] coor-
dination environment. Each hexa-coordinated CuIJII) center
is ligated by two nitrogen atoms (N5, N5#1 for Cu1 and N4,
N4#2 for Cu2) from two L1 ligands and four oxygen atoms
(O7, O7#1, O8 and O8#1 for Cu1 and O6, O6#2, O8 and O8#1
for Cu2) from four coordinated water molecules, respectively
(Fig. 6a). It is interesting to note that the two Cu atoms lie
on inversion centres. The Cu–O bond lengths are 1.986(16)
Å and 2.388(15) Å for Cu1 and 1.983(16) Å and 2.378(14) Å
for Cu2, whereas the Cu–N bond lengths are 2.045(14) Å for
of the ESI†). The last type shows
O17:κN14:κN15:κN16 coordination mode (mode
a
μ4-κO16,
in
H
Scheme 3) to link two Cu1, one Cu2 and one Cu3 with a dihe-
dral angle of 37.21° (Fig. S3i of the ESI†). The μ3-H2O mole-
cule links one Cu1, one Cu2 and one Cu3 that are meanwhile
coordinated by nitrogen atoms of the tetrazole rings to con-
stitute a [Cu3IJH2O)IJN4C)3] trinuclear cluster with the distance
of 0.572 Å to the plane made up of one Cu1, one Cu2 and
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Fig. 4 (a) Coordination environment of CuIJII) ions in 4, symmetry code: #1 −x, −y, −z + 2; #2 −x, −y + 1, −z + 1; #3 −x − 1, −y, −z + 1; #4 −x, −y + 1,
−z + 2; #5 −x + 1, −y + 1, −z + 2; #6 x + 1, y + 1, z. (b) The infinite 1D chain formed from trinuclear metallic clusters. (c) View of the complicated 3D
framework of 4. (d) Schematic representation of the (4,4,8)-connected topology of (46)2IJ412·612·84).
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Fig. 5 (a) Coordination environment of CuIJII) ions in 5, symmetry code: #1 −x + 2, −y, −z; #2 −x + 1, −y, −z; #3 −x + 3, −y, −z + 1. (b) The wave-
shaped zigzag chain formed from trinuclear metallic clusters. (c) The view of the 2D network. (d) Schematic representation of the 3-connected to-
pology of (63).
Cu1 and 2.049(15) Å for Cu2 (Table S1†). The L1 ligands
having a dihedral angle of 25.28° (Fig. S3j of the ESI†) in a
bis-monodentate fashion (mode F in Scheme 3) identical to
that of the first type in 5 connect Cu1 and Cu2 to form a
1D chain as side arms strengthened by the coordinated wa-
ter molecules with five-membered rings having the shortest
Cu1⋯Cu2 distance of 3.915(15) Å (Fig. 6b).
[Ag2IJL2)]n (7). Complex 7 exhibits a 3D framework based
on L2 ligands and AgIJI) ions and crystallizes in the ortho-
rhombic space group Ama2. The value of its Flack parameter
is [0.5(2)] showing that the crystal may be racemic. The asym-
metric unit consists of two crystallographically independent
AgIJI) ions and one L2 ligand. As shown in Fig. 7a, Ag1 on a
mirror plane exhibits
a
distorted tetragonal pyramidal
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Fig. 6 (a) Coordination environment of CuIJII) ions in 6, symmetry code: #1 −x + 1, −y, −z; #2 −x, −y, −z; #4 x + 1, y, z. (b) The view of the infinite 1D
chain.
geometry formed by two nitrogen atoms (N4, N4#1) from two
different L2 ligands and three oxygen atoms (O2#2, O4, O7)
from three different L2 ligands. Ag2 on a twofold axis adopts
a distorted tetrahedral geometry surrounded by two nitrogen
atoms (N5, N5#3) from two different L2 ligands and two oxy-
gen atoms (O3#4, O3#5) from two different L2 ligands. The
Ag–N bond distances are 2.188(13) Å and 2.293(16) Å, and the
Ag–O bond lengths range from 2.541(19) to 2.718(33) Å. The
completely deprotonated L2 ligand lying (slightly disordered)
about another mirror plane in 7 manifests one coordination
mode (mode I in Scheme 3), and two aromatic rings in each
ligand are completely perpendicular and rotate away with a
dihedral angle of 99.00° (Fig. S3k of the ESI†). Ag2 ions are
linked by L2 ligands to generate a single 3D network
(Fig. 7b), composed practically of 32-membered rings
(Fig. 4b). When Ag1 ions are introduced into the network, the
final obtained 3D structure exhibits a complicated framework
(Fig. 7c) that is also constructed from Ag2 ions and another
single 3D framework generated by coordination interactions
of Ag1 ions and ligands. On the basis of the above, Ag1 bind-
ing five L2 ligands can be perceived as a 5-connected node,
[Ag8IJL3)4IJH2O)]n (8). Complex 8 is a 2D framework and
¯
crystallizes in the triclinic space group P1. The asymmetric
unit consists of four AgIJI) ions, two L3 ligands and one
coordinated water molecule. In Fig. 8a, Ag1 and Ag3 are
two-coordinated with two nitrogen atoms (N6, N12) from
two different ligands for Ag1 and two nitrogen atoms (N3,
N9#4) from two different ligands for Ag3. Ag2 and Ag4 are
five-coordinated exhibiting a distorted trigonal bipyramid
with two nitrogen atoms (N4, N5#2) from two different li-
gands and three oxygen atoms (O5#3, O6#2, O7#2) from an-
other two different ligands for Ag2 and one nitrogen atom
(N10), three oxygen atoms (O4, O5#3, O6#2) from two dif-
ferent ligands and one oxygen atom (O11#1) from one co-
ordinated water molecule for Ag4, as displayed in Fig. 8b.
All Ag–N bond lengths fall in the range of 2.140IJ4)–
2.330IJ4) Å, and the Ag–O bond lengths vary from 2.303(3)
to 2.576(3) Å, both falling in normal ranges. The ligands
adopt two different coordination modes: one type with a
dihedral angle of 52.14° (Fig. S3l of the ESI†) links one
Ag1, three Ag2, one Ag3 and one Ag4 with a μ6-κO4,
O5:κO5:κN3:κN4:κN5:κN6 coordination mode (mode J in
Scheme 3), and the other with a dihedral angle of 43.40°
(Fig. S3m of the ESI†) links one Ag1, one Ag2, one Ag3
and two Ag4 with a μ5-κO7,O8:κO6:κN9:κN10:κN12 coordi-
nation mode (mode K in Scheme 3). The adjacent Ag1
and Ag3 centers are linked alternately via two tetrazole
rings from two kinds of ligands with the shortest distance
Ag2 coordinating four L2 ligands can be viewed as
a
4-connected node and each L2 ligand bridging nine AgIJI) ions
can be deemed as a 9-connected node. Thus, the resulting
structure of 7 can be classified as a 3-nodal (4,5,9)-connected
new topology which has the point symbol of (45·6)IJ47·63)IJ418
·616·82) (Fig. 7d).
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Fig. 7 (a) Coordination environment of AgIJI) ions in 7, symmetry code: #1 −x + 1/2, y, z; #2 −x + 1, −y + 1, z; #3 −x + 1, −y + 2, z; #4 x, y + 1/2, z +
1/2; #5 −x + 1, −y + 3/2, z + 1/2. (b) View of the 3D network constructed from Ag1 and the ligands. (c) View of the complete 3D framework. (d)
Schematic representation of the (4,5,9)-connected topology of (45·6)IJ47·63)IJ418·616·82).
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Fig. 8 (a) Coordination environment of Ag1 and Ag3 in 8, symmetry code: #4 x, y, z + 1. (b) Coordination environment of Ag2 and Ag4 in 8, symmetry
code: #1 −x + 2, −y + 2, −z; #2 −x, −y + 2, −z + 1; #3 x − 1, y, z. (c) View of the 1D chain constructed from Ag1 and Ag3 and the ligands. (d) View of the 1D
chain constructed from Ag2 and the ligands. (e) View of the 1D chain constructed from Ag4 and the ligands. (f) View of the complete 2D network.
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of 6.379(2) Å to generate a 1D chain (Fig. 8c). Two Ag2 Discussion
centers are linked by two tetrazole rings from one kind of
ligand with the distance of 3.722(2) Å to give a dinuclear
structure, further assembled into an infinite 1D chain by
nitrogen atoms of the tetrazole rings coordinated with the
metal centers (Fig. 8d). Two Ag4 centers are linked by a
pair of ligands with the distance of 5.609(2) Å to give a
dinuclear structure, further assembled into a 1D chain by
coordinated water molecules bridging the metal centers
(Fig. 8e). The above three types of 1D chains interact mu-
tually to form a 2D network (Fig. 8f).
It is well acknowledged that substituents on the benzene
rings not only determine the position of the new substitu-
ents, but also affect the activity of the electrophilic substitu-
tion reaction. The hydroxyl group increases the electron den-
sity of the benzene ring, and the increase of the ortho and
para locations is particularly significant. However, the tetra-
zolyl group decreases the electron density of the ring, and the
lower decrease of electron density of the meta location, under
greater pressure and higher temperatures, can lead to multi-
level nitration reactions. Therefore, this work used three
phenols, 4-(1H-tetrazol-5-yl)phenol, 3-(1H-tetrazol-5-yl)phenol
and 2-(1H-tetrazol-5-yl)phenol, substituted by the tetrazole
rings at different positions to form three ligands, of which
the locations ortho and para to the hydroxyl groups have all
been nitrated, 2,6-dinitro-4-(1H-tetrazol-5-yl)phenol, 2,4,6-
trinitro-3-(1H-tetrazol-5-yl)phenol and 2,4-dinitro-6-(1H-tetra-
zol-5-yl)phenol, by secondary, tertiary and secondary nitra-
tion, respectively, which is consistent with the directing effect
[CuIJL3)IJH2O)2]n (9). Complex 9 is a 1D chain and crystal-
lizes in the monoclinic crystal system with the I2/c space
group. Each asymmetric unit includes one crystallographi-
cally independent CuIJII) ion, one L3 ligand and two coordi-
nated water molecules. The CuIJII) ion displays a distorted
square pyramidal coordination geometry. The basal posi-
tions were occupied by one nitrogen atom (N6) and one ox-
ygen atom (O5) from one deprotonated L3 ligand, one ni-
trogen atom (N4#1) from another deprotonated L3 ligand
and one oxygen atom (O6) from one coordinated water
molecule (Fig. 9a). The apical position was filled with one
oxygen atom (O7) from one coordinated water molecule.
The Cu–N bond lengths are 1.938(10) Å and 1.977(10) Å,
and the Cu–O bond lengths vary from 1.921(9) to 2.403(16)
Å. The L3 ligand with a dihedral angle of 7.75° (Fig. S3n of
the ESI†) in a chelating-monodentate mode (mode L in
Scheme 3) connects CuIJII) ions to generate a 1D chain
forming a five-membered ring having the shortest Cu⋯Cu
distance of 5.8445(15) Å (Fig. 9b).
+
of substituents. All electrophilic reagent NO2 cations come
from the nitrate reagents, and adding concentrated hydro-
chloric acid to the reaction system improves the ability of the
nitrate reagents dissociated into NO2+ cations.
These three ligands can rotate and feature various coordi-
nation conformations during their assembly with metal cen-
ters. The dihedral angles between the tetrazole rings and the
benzene rings in the ligands vary from 3.82° to 90.00°. Com-
plexes 1–6 sharing the same ligands show a 3D framework
for 4 with the topological symbol of (46)2IJ412·612·84) having
Fig. 9 (a) Coordination environment of the CuIJII) ion in 9, symmetry code: #1 −x + 1/2, y − 1/2, −z + 0. (b) View of the infinite 1D chain constituted
by CuIJII) ions and the ligands.
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dihedral angles of 83.69° and 78.94°, a 3D framework for 1
with the topological symbol of (42·6)2IJ44·62·88·10) having a di-
hedral angle of 64.48°, a 2D network for 2 with the topologi-
cal symbol of (43)2IJ46·66·83) having a dihedral angle of 44.29°,
a 2D network for 5 with the topological symbol of (63) having
the biggest dihedral angle of 37.21°, a 1D chain for 6 with a
dihedral angle of 25.28° and a 0D structure for 3 with a dihe-
dral angle of 3.82°. Thus, with the increased degrees of the
dihedral angles in the same ligand, the coordination steric
hindrances of the tetrazole groups gradually decrease, which
results in higher dimensional conformations of the com-
plexes. Accordingly, the dihedral angles between the tetrazole
rings and the benzene rings in the ligands can influence the
dimensional structures of the complexes. In addition, the dif-
ferent structures of 1–3 also indicate that metal ions also play
vital roles in the formation of the complexes. Complexes 4–6
with the same ligands and metal ions display different struc-
tures attributed to the different coordination modes of the li-
gands: coordination modes D and E for 4, coordination
modes F–H for 5 and coordination mode F for 6. The struc-
tural differences of 4 and 5 may also be induced by the differ-
ent mole ratios of the ligand and metal center (1 : 1 for 4 and
1 : 1.5 for 5). Complexes 2, 7 and 8 as well as 5 and 9 using
the same metal salt have different structures attributed to dif-
ferent ligands. In summary, the different positions of the hy-
droxyl and tetrazolyl groups on the aromatic ring vary the ni-
tration degree of the ligands, and the twist angles and
coordination modes of the ligands as well as the proportions
of the ligand and metal center can have significant influences
on constructing structures of complexes.
Fig. 10 UV-vis spectra of 1–9 in the solid state at room temperature.
framework continued to decompose in the temperature range
of 220–800 °C, which may be attributed to the removal of the
ligands. The first weight loss observed for complexes 4–6
corresponded to the loss of the coordinated water molecules,
lattice water molecules or hydroxyl ions. The second weight
loss was due to the loss of the ligands. Complex 9 released
its two coordinated water molecules (obsd 10.69%, calcd
10.30%) in the temperature range of 30–130 °C, and then the
collapse of the network happened at 300 °C, corresponding
to the residual weight of copper oxide (obsd 21.03%, calcd
22.75%).
The solid-state UV-vis spectra and band gap energy
Semiconductor materials are of interest owing to their poten-
tial applications. Therefore, the physicochemical properties
of complexes 1–9 were measured by UV-vis diffuse reflection.
The solid-state UV-vis absorption spectra of 1–9 show a broad
absorption band in the UV and visible regions as shown in
Fig. 10. Complexes 1–9 reveal intense absorption peaks at
240–300 nm ascribed to the π–π* or n–π* transitions of li-
gands. The higher energy bands can be assigned to metal-to-
ligand charge-transfer (MLCT) transitions or ligand-to-metal
PXRD and thermal analyses
The purity of complexes 1–9 was measured by powder X-ray
diffraction (PXRD). The PXRD patterns of as-synthesized com-
plexes 1–9 are coincident with the simulated ones from the
single-crystal data, indicative of their high purity and homo-
geneity (Fig. S4 of the ESI†). To examine the thermal stabili-
ties of these compounds, thermogravimetric analyses (TGA)
were carried out under an argon environment with a heating
rate of 10 °C min−1 from 25 °C to 800 °C (Fig. S5 of the ESI†).
For complex 1, a weight loss was observed from ambient tem-
perature to 230 °C due to the release of one lattice water mol-
ecule and two coordinated hydroxyl ions, then the structure
decomposed from 300 °C. Complexes 2 and 7 exhibited a
one-step weight loss and maintained their stability under 300
°C for 2 and 320 °C for 7, then the frameworks began to de-
compose upon further heating, and the final residual weight
was likely assigned to silver oxide (obsd 49.76%, calcd
49.74% for 2 and obsd 49.45%, calcd 45.36% for 7). Complex
8 showed release of one coordinated water molecule from 80
°C to 160 °C, followed by decomposition at 300 °C, indicating
that the final products obtained were also silver oxide (obsd
49.17%, calcd 49.26%). Complex 3 primitively lost its coordi-
nated water molecules and lattice water molecules (obsd
11.65%, calcd 15.78%) from 50 °C to 180 °C. After that, the
Fig. 11 Emission spectra of 1–3, 7 and 8 in the solid state at room
temperature.
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charge-transfer (LMCT) transitions, and the lower energy
band can be attributed to the spin-allowed d–d* electronic
transitions of the CoIJII) ions and CuIJII) ions.26 The diffuse re-
flectance spectra revealed that the band gap energies of 1–9
are 2.43 eV for 1, 2.21 eV for 2, 2.33 eV for 3, 2.37 eV for 4,
2.25 eV for 5, 2.24 eV for 6, 2.41 eV for 7, 2.22 eV for 8 and
2.46 eV for 9, according to the formula: Eg = 1240/λg (eV),
where Eg is the band gap energy (eV) and λg is the absorption
edge wavelength (nm) (Fig. S6 of the ESI†), which indicates
that 1–9 have potential semiconductor properties.
properties of complexes 1–3, 7 and 8 based on ligands
containing strong conjugated tetrazolyl and phenyl rings
were evaluated in the solid state at room temperature. The
emission spectra are depicted in Fig. 11, and 1–3, 7 and 8 are
found to exhibit green intense emission bands at 545 nm,
571 nm, 550 nm, 544 nm and 565 nm with excitation at 343
nm, 345 nm, 346 nm and 341 nm and 345 nm, respectively
(Fig. S7 of the ESI†). The results suggest that these emission
bands of 1, 2, 7 and 8 are neither ligand-to-metal charge
transfer (LMCT) nor metal-to-ligand charge transfer (MLCT)
in nature because ZnIJII) ions and AgIJI) ions are tough to re-
duce or oxidize due to their d10 configuration but rather
could be chiefly attributed to intraligand transition.28 The
emission enhancement of 1 is also observed compared to
that of 2 most probably deriving from the different local coor-
dination environments around the metal ions.29 In spite of
Luminescence properties
CPs with luminescence properties have attracted considerable
attention because of their potential applications in optical
sensors and light-emitting materials.27 The luminescence
Fig. 12 Temperature-dependent magnetic susceptibilities of 3–6 and 9 in the temperature range of 2–300 K under an applied magnetic field of
1000 Oe.
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CoIJII) ions probably quenching the luminescence emission,30
fortunately, complex 3 shows strong emission due to [4T1gIJF)
which is slightly larger than the spin-only value of 0.38 emu
mol−1 K expected for one CuIJII) ion (S = 1/2, g = 2.00). The
value of χmT decreases as the temperature decreases and de-
scends to 0.14 emu mol−1 K at 2 K, exhibiting a dominant
→
4T1gIJP)] transitions, which is typical of high-spin
hexacoordinated octahedral CoIJII) species, being well in ac-
cord with a previous report,31 and due to the interlayer π–π
stacking and hydrogen bond interactions between aromatic
units.32 This result shows that these complexes may be po-
tential candidates as emitting materials.
Furthermore, the emission decay lifetimes of these com-
plexes were measured at room temperature (Fig. S8 of the
ESI†). The luminescence lifetimes of 1 and 3 are fitted by
biexponential curves with τ1 = 0.60 ns (83.55%) and τ2 = 9.42
−1
antiferromagnetic interaction. The plot of χm versus T fol-
lows the Curie–Weiss law in the range 100–300 K that gives a
Curie constant C = 0.51 emu mol−1 K and a Weiss constant θ
= −47.85 K. The negative θ value for 6 further suggests antifer-
romagnetic properties. For 9, the χmT value is 0.34 emu
mol−1 K at 300 K, which is slightly smaller than the spin-only
value of 0.38 emu mol−1 K expected for one CuIJII) ion (S = 1/2,
g = 2.00). The χmT value reaches a maximum of 0.36 emu
mol−1 K around 150 K and then drops sharply to 0.03 emu
mol−1 K at 2 K, which indicates ferromagnetic interactions
between the CuIJII) ions. At high temperatures, the magnetic
susceptibility obeys the Curie–Weiss law in the range 150–
300 K, giving a positive Weiss constant θ = 14.69 K and C =
0.33 emu mol−1 K, further demonstrating the ferromagnetic
interaction.
ns (16.45%) for 1 as well as τ1 = 0.63 ns (67.10%) and τ2
=
17.24 ns (32.90%) for 3. The luminescence lifetimes of 2, 7
and 8 are fitted by a triexponential curve with τ1 = 5.26 ns
(8.82%), τ2 = 42.57 ns (14.90%) and τ3 = 0.56 ns (76.28%) for
2, τ1 = 5.81 ns (25.59%), τ2 = 41.95 ns (63.14%) and τ3 = 0.69
ns (11.27%) for 7 and τ1 = 6.15 ns (23.29%), τ2 = 50.01 ns
(61.28%) and τ3 = 0.071 ns (15.43%) for 8.
Conclusion
Magnetic properties
We successfully constructed nine new complexes based on
three precursors as well as nitrate salts as nitration reagents
via in situ nitration under different synthetic conditions.
Single-crystal X-ray diffraction analysis revealed that com-
plexes 1, 4 and 7 display 3D frameworks, complexes 2, 5 and
8 show 2D networks, complexes 6 and 9 are 1D chains, and
complex 3 features a mononuclear structure, extending into
2D supramolecular structures by interlayer π–π stacking, and
some main factors that affect the construction of the com-
plexes have been explored. The research on the solid-state
UV-vis spectra and band gap energy of complexes 1–9 indi-
cates that they have potential semiconductor properties. The
research on the solid-state luminescence properties of com-
plexes 1–3, 7 and 8 illustrates that these complexes may be
potential candidates in the optical area. The research on
magnetic measurements suggests that complexes 3–6 show
antiferromagnetic properties and complex 9 shows ferromag-
netic properties.
The magnetic measurements of complexes 3–6 and 9 were
carried out on a SQUID MPMS-XL-7 with an applied magnetic
field of 1000 Oe and in the temperature range of 2–300 K.
−1
Magnetic data as plots of χmT and χm versus T are depicted
in Fig. 12. For 3, the maximum χmT value at 300 K is about
2.52 emu mol−1 K, which is larger than the spin-only value
for magnetically isolated systems with S = 3/2 (1.88 emu
mol−1 K), as expected for a CoIJII) system with a significant
contribution from the unquenched orbital momentum in an
octahedral ligand field.33 Upon cooling, χmT smoothly de-
creases and reaches 1.46 emu mol−1 K at 2 K, indicating that
antiferromagnetic interactions occurred. The magnetic sus-
ceptibility χm−1 versus T obeys the Curie–Weiss law at 100–300
K, which gives C = 2.59 emu mol−1 K and θ = −8.28 K. The
negative θ further confirms antiferromagnetic interactions.
For 4, the χmT value is 0.86 emu mol−1 K at 300 K, which is
smaller than the theoretical value of 1.13 emu mol−1 K for
the three CuIJII) ions (S = 1/2, g = 2.00). Upon cooling, the χmT
value gradually increases to a minimum value at 2 K with
0.11 emu mol−1 K, indicating the presence of antiferromag-
netic properties. The magnetic susceptibility (χm−1) follows
the Curie–Weiss law with C = 1.33 emu mol−1 K and θ =
−172.10 K in the range 100–300 K, and the negative θ further
indicates antiferromagnetic interactions. For 5, the χmT value
at 300 K is 1.90 emu mol−1 K, which is much smaller than
the expected value (2.63 emu mol−1 K) of seven magnetically
isolated spin-only CuIJII) ions (S = 3/2, g = 2.0). When the tem-
perature decreases from 300 to 2 K, the χmT value continu-
ously decreases and reaches a local minimum of 0.71 emu
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (No. 21361026).
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