Combination of N-Arylstilbazolium Organic Nonlinear Optical Chromophores with Iodoargentates: Structural Diversities and Optical Properties

Article abstract of DOI:10.1021/acs.cgd.8b00033

A combination of N-arylstilbazolium organic nonlinear optical chromophores with iodoargentates results in five new hybrids, i.e., [(DAST)(Ag₂I₃)]_n (1), [(DMAQS)(Ag₂I₃)]_n (2), [(DPAS)(Ag₂I₃)]_n (3), [(DPTAS)₂(Ag₅I₇)]_n (4), and [(CEMAS)₂(Ag₅I₇)]_n (5). Among them, the former four are centrosymmetric, and 5 is non-centrosymmetrical (space group Pna2₁) with the introduction of a cyano group in an organic chromophore. The (Ag₅I₇)_n^2n- chains in 4 and 5 are special, in which that of 4 is constructed from Ag₅I₁₀ building blocks with a μ₆-I σ-bonding to six Ag ions, and that in 5 is the connection of a cubane-like Ag₄I₄ core with bridged AgI₄ tetrahedra. UV/vis/near-IR adsorptions and near-IR photoluminescences have been observed. All the organic chromophores are stacked as head-to-tail arrangements, resulting in second harmonic generation (SHG) inactive in 1-4. But 5 is SHG active without J-aggregation of organic chromophore, whose symmetry break was driven by the formation of hydrogen bonds around the cyano group. The SHG activity of 5 originates from the polarizations of the asymmetric contribution of Ag₅I₉^4- unit mixing with non-centrosymmetrical (CEMAS)₂²⁺ pair. Theoretical calculations were carried out to disclose their electronic structures.

Full text of DOI:10.1021/acs.cgd.8b00033

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Article
Combination of N-Arylstilbazolium Organic Nonlinear Optical Chromophores
with Iodoargentates: Structural Diversities and Optical Properties
Yu-Kang Wang, Li-Ming Zhao, Yu-Qing Fu, Zhao Chen, Xiao-
Yan Lin, Dao-Hua Wang, Yi Li, Hao-Hong Li, and Zhi-Rong Chen
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00033 • Publication Date (Web): 31 May 2018
Downloaded from http://pubs.acs.org on May 31, 2018
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Combination of NꢀArylstilbazolium Organic Nonlinear
Optical Chromophores with Iodoargentates: Structural
Diversities and Optical Properties
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YuꢀKang Wang,† LiꢀMing Zhao,† YuꢀQing Fu,† Zhao Chen,† XiaoꢀYan Lin,† DaoꢀHua
†
†
‡
†
†
Wang, Yi Li, HaoꢀHong Li, * ZhiꢀRong Chen *
†College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China.
‡State Key Laboratory Breeding Base of Photocatalysis, Fuzhou University, Fuzhou 350002,
China
ABSTRACT: Combination of Nꢀarylstilbazolium organic nonlinear optical chromophores with
iodoargentates results in five new hybrids, i. e., [(DAST)(Ag2I3)]n (1), [(DMAQS)(Ag2I3)]n (2),
[(DPAS)(Ag2I3)]n (3), [(DPTAS)2(Ag5I7)]n (4) and [(CEMAS)2(Ag5I7)]n (5). Among them, the
former four are centrosymmetric, and 5 is noncentrosymmetrical (space group Pna21) with the
introduction of cyano group in organic chromophore. The (Ag5I7)n2nꢀ chains in 4 and 5 are special,
in which that of 4 is constructed from Ag5I10 building blocks with a µ6ꢀI σꢀbonding to six Ag ions,
and that in 5 is the connection of cubaneꢀlike Ag4I4 core with bridged AgI4 tetrahedra.
UV/Vis/nearꢀIR adsorptions and nearꢀIR photoluminescences have been observed. All the organic
chromophores are stacked as headꢀtoꢀtail arrangements, resulting in second harmonic generation
(SHG) inactive in 1ꢀ4. But 5 is SHG active without Jꢀaggregation of organic chromophore, whose
symmetry break was driven by the formation of hydrogen bonds around cyano group. The SHG
4ꢀ
activity of 5 originates from the polarizations of the asymmetric contribution of Ag5I9 unit
mixing with noncentrosymmetrical (CEMAS)22+ pair. Theoretical calculations were carried out to
disclose their electronic structures.
INTRODUCTION
The discovery of new materials possessing photovoltaic conversion, stimuliꢀresponsive
chromism, magnetic or nonlinear optical (NLO) properties have attracted considerable interests in
the last decade.1ꢀ4 So far, great effort has been paid to the organic functional materials due to their
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structural tenability and fascinating optical properties such as optical signal processing and THz
generation.5ꢀ8 In this field, particularly interests were paid to the organic molecular crystalline
materials due to advantages of high chromophore number density and excellent longꢀterm
orientational stability.9ꢀ11 Stilbazoliumꢀtype πꢀdelocalized molecules have exhibited the largest
molecular hyperpolarizability (β) because of their unique structures with an electron acceptor
linked to an electron donor group via a πꢀconjugated bridge.12 A typical stilbazolium is
4ꢀN,Nꢀdimethylaminoꢀ4'ꢀN'ꢀmethylꢀstilbazolium tosylate (DAST), which has exhibited good
secondꢀorder nonlinear optical activity (103 times of the urea) owing to its outstanding NLO
susceptibilities (d11 >1000 pm/V)), large electroꢀoptic coefficients (r111=77 pm/V), low dielectric
constants (ε1=5.1).12ꢀ15 Hence, many stilbazolium derivatives with similar architectures such as
DSTMS and DSNS have been investigated.16ꢀ17
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However, the observation of bulk nonlinear susceptibility (χ(2)) using these chromophores
depends on their parallel alignment with a noncentrosymmetric arrangement in the crystal. The
control of alignment of the organic molecules in the solid state is still a big challenge,18 and great
efforts have been devoted to the achievement of noncentrosymmetric arrangements of
chromophores. Up to now, the most commonly used strategy is the introduction of various organic
counterꢀanions to get noncentrosymmetric arrangements,8,16,19ꢀ27 such as tosylate derivatives
(2ꢀnaphtalenesulfonate and 2,4,6ꢀ(trimethylbenzenesulfonate),16,19 tetracyanoquinodimethane.20 In
addition, recently, metal complexes were also utilized due to their large polarizability, which can
be divided into following types: (a) monoꢀnuclear metal complexes, for example, [Ni(dmit)2]ꢀ,28
[MIII2M'II(C2O4)6]4ꢀ (M =Rh, Fe, Cr; M' = Mn, Zn) mixed metal oxalates,29 Au(CN)2ꢀ 30 and MPS3
(M=Mn, Cd, Zn);31ꢀ33 (b) polymeric metal halides;34ꢀ37 (c) polyoxometalates.38 But these methods
are also low efficiency in the control of chromophore aggregation modes, because they only
modify the structure of one moiety.
Inorganicꢀorganic hybrids pave a new way for the design of new nonlinear optical materials,
because they can provide the modification method in both organic and inorganic moeities. In
organic chromophore, different substituents can be introduced to induce their aggregation modes,
and in inorganic moieties, high polarizability components can be incorporated. For example,
iodoargentates polymers with high covalent feature of the Ag−I bond and possible existence of
Ag···Ag interactions will give rise to high polarizability.39 To the best of our knowledge, the study
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about the combination of NLOꢀphore chromophores with iodoargentates is rare.35 In this work, by
introducing different substituents on NLOꢀphore chromophores, we obtain five chromophores
and combine them with iodoargentates to afford five new NLOꢀphore chromophore/iodoargentates
hybrids, namely, [(DAST)(Ag2I3)]n (1), [(DMAQS)(Ag2I3)]n (2), [(DPAS)(Ag2I3)]n (3),
[(DPTAS)2(Ag5I7)]n (4) and [(CEMAS)2(Ag5I7)]n (5). Among them, 5 is second harmonic
generation (SHG) active with a response as one time as that of KDP (potassium dihydrogen
phosphate). This work provides an example of NLO active solid without Jꢀaggregation of organic
chromophore, in which the symmetry break was driven by the formation of hydrogen bonds
around cyano group. Theoretical calculations were carried out to correlate the structureꢀproperty
relationships.
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EXPERIMENTAL SECTION
Materials and Methods All chemicals were of reagent grade quality obtained from commercial
sources and used without further purification. IR spectra were recorded on a PerkinꢀElmer
Spectrumꢀ2000 FTIR spectrophotometer (4000ꢀ400cmꢀ1) on powdered sample spread on KBr
plate. Elemental analyses for C, H and N were performed on a Vario MICRO elemental analyzer.
Purities of the grown crystals were confirmed by the Xꢀray powder diffraction (PXRD) performed
on a Philips X’PertꢀMPD diffractometer with CuKα radiation (λ = 1.54056 Ǻ). Optical diffuse
reflectance spectra were measured on a Aglient Carry 5000 UV/Vis/nearꢀIR spectrophotometer
equipped with an integrating sphere at 293 K and BaSO4 plate used as a reference in the range of
200ꢀ2500 nm. The absorption spectra were calculated from reflectance spectra using the
Kubelka−Munk function: α/S = (1 − R)2/(2R), where α is the absorption coefficient, S is the
scattering coefficient, and R is the reflectance.40 Fluorescence spectra were characterized by a
1
Edinburgh FLꢀFS 920 TCSPC spectrometer in solid state. H NMR and 13C NMR spectra were
recorded at a Bruker AVIII 400 spectrometer, whose chemical shifts were reported in parts per
million (ppm) downfield from tetramethylsilane.
NLO Experiments Nonlinear optical properties were confirmed by the Kurtz and Perry
technique,41 that is, the secondꢀharmonic (SHG) powder test. The ground microcrystalline
powdered samples were filtrated with different sizes and placed between two glass plates with a
thickness of 2 mm. The measured SHG signals were converted into the measurable signal voltage
with the fundamental beam being removed by appropriate filters. The collected digital signals
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were then investigated by a photomultiplier and displayed with a DS1052E digital oscilloscope
with respect to the corresponding powdered KDP with the same particle sizes of 300−350 ꢁm as
reference. A Qꢀswitching laser with a wavelength of 2.0 ꢁm was used as fundamental radiation to
determine the SHG efficiency.
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Computational Details The cif files of 1−5 were used to construct the calculated models. The
electronic structure calculations were carried out using density functional theory (DFT) with the
three nonꢀlocal gradientꢀcorrected exchange−correlation functions (GGAꢀPBE) and using
CASTEP code,42 which uses a plane wave basis set for the valence electrons and normꢀconserving
pseudopotential for the core electrons.43 The number of plane waves included in the basis was
determined by a cutoff energy Ec of 550 eV. Pseudoatomic calculations were performed for Ag
4s24p64d105s1, I 5s25p5, C 2s22p2, N 2s22p3, and H 1s1. The parameters used in the calculations and
convergence criteria were according to the default values of the CASTEP program in Materials
Studio 8.0.
The gas structures of five organic chromophores were optimized at B3LPY/6ꢀ31g(d) level
using Gaussian 09 program package.44 Besides, DFT calculations were carried out to disclose the
magnitude and direction of the dipole moments of the Ag5I94ꢀ building block and (CEMAS)22+ pair
4ꢀ
in the asymmetric unit using the Gaussian 09. During the calculations, Ag5I9 building block
2nꢀ
constructed from Ag4I4 cubane and bridged AgI4 tetrahedron was used to simulate the (Ag5I7)n
chain of 5. The calculations were performed by using spin restricted DFT wave functions B3LYP.
The 6ꢀ31g(d) basis set was used for C, N and H atoms, while lanl2dz basis set was employed for
the Ag and I atom.
Synthesis
Synthesis of organic chromophores: All organic chromophores, 4′ꢀdimethylaminoꢀNꢀmethyl
stilbazolium (DAST)·I, 4′ꢀdimethylaminoꢀNꢀmethylquinolin stilbazolium (DMAQS)·I,
4′ꢀdiphenylaminoꢀNꢀmethyl stilbazolium (DPAS)·I, 4′ꢀ(4ꢀdiꢀpꢀtolylamino)ꢀNꢀmethyl stilbazolium
(DPTAS)·I, 4′ꢀ(4ꢀ(2ꢀcyanoethyl)(methyl)amino)ꢀ Nꢀmethyl stilbazolium (CEMAS)·I were
synthesized by Knoevenagel reaction methods using DeanꢀStark apparatus (scheme 1), which
have been recrystallized two times in order to obtain purer products.6 We set (DAST)·I as example:
4ꢀpicoline (0.9300 g, 10 mmol), methyl iodide (1.4200 g, 10 mmol) were refluxed for 12 hours in
methanol
solvent
for
producing
1,4ꢀdimethylpyridinꢀ1ꢀium
iodide,
and
then
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4ꢀN,Nꢀdimethylaminoꢀbenzaldehyde (1.4900 g, 10 mmol) was added in the presence of piperidine
(5 drops) as catalyst. The solution was continued refluxing for 12 hours to get final products. The
1H NMR, 13C NMR spectra and their assignments of five chromophores can be seen in Fig. S1ꢀ5
(Supporting Information).
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CH3
CH3
N
+
N
+
H3C N
CH3
H3C
N
CH3
+
+
DAST
DMAQS
CH3
N
N
+
+
H3C N
H3C N
+
DPAS
+
DPTAS
CH3
CH2CH2CN
CH3
N
+
H3C
N
+
CEMAS
Scheme 1 The structure of NꢀArylstilbazolium organic nonlinear optical chromophores
Crystal growth
[(DAST)(Ag2I3)]n (1): 1 was prepared by solution low evaporation method. (DAST)·I (0.0366 g,
0.1 mmol) was dissolved in 4 mL CH3CN solvent. In another flask, AgI (0.0353 g, 0.15 mmol)
and KI (0.0664 g, 0.4 mmol) were dissolved in 6 mL DMF and stirred for 30 min. The former
solution was dropped into the latter slowly and kept stirring for another 30 min, afterwards the pH
value of resultant solution was adjusted to 6.0 using 10% HI solution. The obtained solution was
filtered and red filtrate liquor was kept at room temperature for slow evaporation. Block black
crystals were obtained after the growth period of 1 week. Yield: 30.5% (0.0192 g, based on Ag).
Anal. Cald. for C16H19Ag2I3N2 (835.77): calcd. C 22.99, H 2.29, N 3.35 %; found C 22.85, H 2.20,
N 2.26 %. IR (cmꢀ1): 3046(w), 2902(w), 1643(m), 1566(s), 1506(s), 1370(m), 1154(s), 1038(m),
939(m), 864(m), 800(m), 721(m).
[(DMAQS)(Ag2I3)]n (2): 2 was prepared by solvothermal method. ((DMAQS)·I (0.0418g, 0.1
mmol), AgI (0.0235 g, 0.10 mmol) and KI (0.0332 g, 0.2 mmol) were dissolved in 10 mL CH3CN
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and then transferred them to a Teflon jar (25 mL). The solution was stirred for 30 min at room
temperature to become homogeneous, and the Teflon jar with the reactant was put into the steel
sleeve and tightened the cover. The autoclave was heated to 120°C at a rate of 30°C per hour and
held at this temperature for 72 h, afterwards the autoclave was cooled to room temperature with
cooling rate of 2 °C per hour. The black crystals were washed three times with ethanol and dried at
room temperature. Yield: 33.2% (0.0147 g based on Ag). Anal. Cald. for C20H21Ag2I3N2 (885.83):
calcd. C 28.47, H 2.39, N 3.16 %; found C 28.60, H 2.24, N 3.09 %. IR (cmꢀ1): 3076(s), 2899(w),
1523(s), 1324(m), 1165(m), 1104(m), 966(s), 819(s), 751(s), 512(s).
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[(DPAS)(Ag2I3)]n (3): The synthesis process of
3 was similar to that of 1, except that (DPAS)·I
(0.0490 g, 0.1mmol) was used as starting organic chromophore. Block black crystals were
obtained after one week. Yield: 28.4% (0.0204 g, based on Ag). Anal. Cald. for C26H26N2Ag2I3
(959.90): calcd. C 32.53, H 2.71, N 2.92%; found C 32.45, H 2.73, N 2.94 %. IR (cmꢀ1): 3056(w),
1569(s), 1485(s), 1292(m), 1164 (s), 967(m), 830(s), 750(s), 693(s), 535(s).
[(DPTAS)2(Ag5I7)]n (4): The synthesis of
4 was the same with that of 2, except that the type and
amount of starting materials differ to some extent. (DPTAS)·I (0.0518g, 0.1 mmol) and AgI
(0.0352 g, 0.15 mmol) were dissolved in 10 mL CH3CN. The autoclave was cooled to room
temperature within 24 hour. The obtained black crystals were washed three times with ethanol and
dried at room temperature. Yield: 27.3% (0.0181 g based on Ag). Anal. Cald. for C56H54Ag5I7N4
(2210.68): calcd. C 30.42, H 2.55, N 2.53%; found C 30.60, H 2.44, N 2.69%. IR (cmꢀ1 ): 3027(w),
2919(w), 2250(w), 1896(w), 1582(s), 1500(s), 1320(s), 1265(s), 1175(s), 963(s), 815(s), 714(s),
532(s).
[(CEMAS)2(Ag5I7)]n (5): The synthesis details of
5 was similar to that of 2, in which (CEMAS)·I
(0.0418g, 0.1 mmol) was used as starting organic chromophore. The autoclave was heated to
160 °C at a rate of 40°C per hour and held at this temperature for 72 h, afterwards the autoclave
was cooled to room temperature in 48 h. The dark red stick crystals were washed three times with
ethanol and dried at room temperature. The sizes, sharps and colors of asꢀsynthesized crystals
were shown in Fig. S6 (Supporting Information). Yield: 35.7% (0.0142 g based on Ag). Anal. Cald.
for C36H40Ag5I7N6 (1984.39): calcd. C 21.79, H 2.03, N 4.23 %; found C 21.72, H 2.20, N 4.33 %.
IR (cmꢀ1): 3035(s), 2902(w), 2242(m), 1641(s), 1572(s), 1518(s), 1379(m), 1312(m), 1248(m),
1161(s), 1112(s), 1037(s), 966(m), 827(m).
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Xꢀray crystallography The intensities of five crystals were all collected on a Bruker APEX II
diffractometer using graphiteꢀmonochromated MoKα radiation (λ = 0.71073 Å) at room
temperature by using ω/2θ scan mode. The empirical absorption corrections were based on
equivalent reflections. Structures were solved by direct method followed by successive difference
Fourier methods. Computations were performed using SHELXTL and final fullꢀmatrix
refinements were against F2.45,46 All nonꢀhydrogen atoms were refined anisotropically. Hydrogen
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atoms of CꢀH were generated geometrically. The relative high residual peaks of
5 locate at around
Ag atoms (1.36 and 0.43 Å from Ag(3)), suggest that they are dummy peaks. Crystallographic
data and refinement details are listed in Table 1. Selected bond distances and angles of 1ꢀ5 are
given in Table S1 and S2, hydrogen bond parameters are shown in Table S3, π–π stacking
interactions are summarized in Table S4 (Supporting Information). Crystallographic data have
been deposited at the Cambridge Crystallographic Data Center as supplementary publications.
RESULTS AND DISCUSSION
Description of structures
nꢀ
Compound
1
ꢀ3
all contain 1ꢀD anionic chains with formula of (Ag2I3)n and corresponding
nꢀ
Nꢀarylstilbazolium organic nonlinear optical chromophores. The formula of (Ag2I3)n chains in
iodoargentate system are commonly observed, for example, (Habtz)(Ag2I3), (HCP)(Ag2I3),
(MC)(Ag2I3).3,35,47ꢀ49 But their structures differ to some extent due to the different linkage modes
of AgI4 tetrahedra. The asymmetric units of
Nꢀarylstilbazolium cation. All Ag centers are in distorted tetrahedral geometries with four I donors
without taking AgꢀAg bond into account. For , each Ag center is bound to two ꢁ2ꢀI and two ꢁ4ꢀI
atoms, and in and , Ag ions are coordinated by one ꢁ2ꢀI and three ꢁ3ꢀI atoms. The Ag−(ꢁ2ꢀI)
1ꢀ3 contain two Ag atoms, three I atoms and one
1
2
3
(2.7629(11)−2.8482(12) Å), Ag−(ꢁ3ꢀI) (2.8217(22)−3.1979(13) Å) and Ag−(ꢁ4ꢀI) (2.9240(15)−
3.0399(17) Å) bond lengths, and their corresponding I−Ag−I bond angles (91.72(2)−130.13(3)°)
nꢀ
nꢀ
are consistent with those of the other reported (Ag2I3)n chains (Table S1, S2). 35 The (Ag2I3)n
chain in can be discussed in terms of Ag2I6 unit, which is constructed from two edgeꢀsharing
1
AgI4 tetrahedra. In this Ag2I6 unit, argentophilic interaction is present judged from the Ag···Ag
separation (3.148(2) Å, shorter than the sum of van der Waals radius of silver 3.44 Å). Adjacent
Ag2I6 units are linked into a 1ꢀD straight line chain along cꢀaxis via sharing four edges (Fig. 1a),
49
which is structural similar to {[Er(DMF)8][Ag6I9]}n
.
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The (Ag2I3)nnꢀ chain in
2
and
3
are isostructures build from Ag4I8 units, which are defined by
5
four edgeꢀsharing AgI4 tetrahedra. Here only we set
2 as example. Versatile argentophilic
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interactions can be observed with Ag···Ag separations of 3.0004(18)−3.1294(13) Å, upon which a
planar Ag4 rhomboid is given. The bridged I atoms locate at two sides of the Ag4 rhomboid.
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Furthermore, neighboring Ag4I8 units are connected into a 1ꢀD straight chain along aꢀaxis by
sharing the same edges (Fig. 2a and Fig. S7(a)).
2nꢀ
Compound
4 and 5 are composed by a 1ꢀD (Ag5I7)n chains and two crystallographically
independent organic (DPTAS)+/(CEMAS)+ chromophores. The formula of (Ag5I7)n2nꢀ chains have
also been frequently documented, for example, [Mn(phen)3](Ag5I7) and
But their real structures also differ with each other greatly. The
50,51
{[Et3N(CH2)6NEt3][Ag5I7]}n.
2nꢀ
(Ag5I7)n chain in
4
is unique due to the presence of interesting 2+2 AgI4 planar square
is termed as Ag5I10 unit (Fig. 3a). In this Ag5I10 unit,
geometries. In detail, the building block of
4
Ag(2), Ag(2)#2, Ag(3), Ag(3)#2 (#2: ꢀx+1/2,y,ꢀz+1/2) are in tetrahedral environments with four I
donors, and the AgꢀI bond lengths and angles are comparable to those of AgI4 tetrahedra in other
hybrid iodoargentates.50,51 But coordinated environment of Ag(1) is unique with two short
(2.7954(9) Å) and two long (3.2748(3), 3.3944(3) Å) AgꢀI bonds. If two long AgꢀI bonds are not
considered, the Ag(1) center is in linear geometry. But when two weak AgꢀI bonds (semiꢀbonds)
are taken into account, Ag(1) center is in planar square environment. Therefore, the coordinated
environment of Ag(1) can be treated as a 2+2 planar square environment. Abundant Ag···Ag
interactions can be observed with distances of 3.041(2)−3.183(2) Å (Table S2). Based on these
Ag···Ag interactions, five Ag atoms and six I atoms are generally coꢀplanar with deviation less
than 0.0012 Å. I(1), I(4) locate at both sides of this plane. In addition, the relatively higher thermal
parameter of Ag(1) (0.23913) also suggests its relaxed coordinated environment, where Ag(1) is
encapsulated in the cavity defined by Ag4I10 unit. Neighboring Ag5I10 units are connected into a
1ꢀD straight line chain along
b
ꢀaxis via edgeꢀsharing fashion (Fig. 3b). Consequently, a
µ6ꢀI(2) is
observed locating at the center of the hexagonal and
σ
ꢀbonding to six Ag atoms. This kind of
condensation modes has not been reported in hybrid iodoargentates until now.
2nꢀ
The (Ag5I7)n of
5 is a zigzagꢀlike chain built from cubaneꢀlike Ag4I4 nodes. The distorted
cubaneꢀlike Ag4I4 core is similar with typical Mo–S cubane, which have been commonly observed
in iodoargentates system. Based on Ag4I4 cubane, 0ꢀD clusters (for instances,
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(Y(DMSO)7)(Ag4I8)3),52 1ꢀD chains ([(APHENꢀH)2(Ag4I6)]n),53 2ꢀD layers (such as
{[PC]2[Ag4I6]}n),48 and 3ꢀD open frameworks ({[BCP]2[Ag4I6]}n) 48,54 of iodoargentate hybrids
have been documented. But the linkage mode of cubaneꢀlike Ag4I4 core in the (Ag5I7)n2nꢀ chain of
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differs greatly. In detail, each Ag4I8 unit containing cubaneꢀlike Ag4I4 core connects with
neighboring units via bridged AgI4 tetrahedra and I atoms to give a 1ꢀD zigzagꢀlike chain along
ꢀaxis (Fig. 4a). Consequently, abundant Ag···Ag interactions with separations among 2.978(2)−
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a
3.318(2) Å are observed, indicating the presence of strong argentophilic interactions.
The structural parameters of organic chromophores are summarized in Table 2 (DAST+ was
set as example and shown in Fig. 1b). The leastꢀsquares analysis showed that the dihedral angles
between pyridine ring and benzene ring are 1.78−13.28°, indicating that two planes (pyridine and
benzene rings) are approximately coplanar. Among them DMAQS+ in
5 exhibits the largest
dihedral angle of 13.28°, which might be driven by the formation of hydrogen bonds. The sum of
the three C–N–C angles taking N atoms as centers are all close to 360.0°, suggesting that
outstretched methyl and carbon atoms of Nꢀsubstituents are generally coꢀplanar. These coplanar
natures illustrate that the πꢀelectrons in the organic chromophores are delocalized. The bond
lengths of C–C based on the benzene and pyridine rings range between the C–C single bond
(1.524 Å) and C–C double bond (1.317 Å), indicating that the bond lengths are even. All the
organic chromophore exists in the trans Eꢀconfiguration with respect to the ethenyl double bonds
(bond distances: 1.30(2)−1.339(14) Å) with the torsion angle of 175.1(4)−178.9(6)°. Compared
with the free organic chromophores (optimized at B3LYP/6ꢀ31g(d) level), only slight structural
adjustments on dihedral angles between pyridine ring and benzene ring have happened, which
might be led by weak interactions with iodoargentates.
There are no classic hydrogen bonds and π···π stacking can be found in
1 and 3, and only
electrostatic interactions contribute to the structural stabilization (Fig.1c, Fig. S7b). But in
2
,
strong faceꢀtoꢀface π···π stacking interactions among headꢀtoꢀtail arranged DMAQS+ are observed
(Fig. 2b, Table S4). Interestingly, intermolecular CꢀH···N and CꢀH···I hydrogen bonds are present
in
4 and 5, which contribute to the structural stabilization. The H···I distance in the range of
2.94−2.96 Å and C−H···I angles in the range of 150−151° are in agreement with the values
reported in the literature (Table S3, Supporting Information).3 In detail, in
4
, C(6)ꢀH(6)···I(2)
hydrogen bond can be found between pyridine ring and µ6ꢀI(2), which extends the 1ꢀD chain to be
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a 2ꢀD layer along abꢀplane (Fig. 3c). And in
5
, two CꢀH···N intermolecular hydrogen bonds are
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given. The first is between methyl CꢀH on pyridine in one crystallographically independent
(CEMAS)+ꢀ1 cation (defined by N(4)ꢀN(5)ꢀN(6)) and the cyano group on the other (CEMAS)+ꢀ2
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2+
cation (defined by N(1)ꢀN(2)ꢀN(3)), upon which an unꢀsymmetric (CEMAS)2 pair with
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2+
headꢀtoꢀtail arrangement is generated. In this (CEMAS)2 pair, π···π stacking interactions
between pyridine and benzene rings are observed (Fig. 4b). Furthermore, unꢀsymmetric
(CEMAS)22+ pairs interact with each other via CꢀH(benzene)ꢀcyano group hydrogen bond to give
2n+
a 1ꢀD (CEMAS)2n chain along cꢀaxis (Fig. 4b). Finally, C(29)−H(29)···I(2) hydrogen bond
between (Ag5I7)n2nꢀ and (CEMAS)2n2n+ chains gives rise to the soꢀcalled hybrid structure (Fig. 4c).
All the πꢀconjugated organic chromophores are arranged themselves in headꢀtoꢀtail fashion
(the pyridinium as head and trimethylammonium as tail) with alternating directionality due to the
strong ‘push–pull’ electron nature.36 Consequently, 1ꢀ4 crystallize in centrosymmetric space
groups. But in
5, due to the presence of cyano group as a strong hydrogen acceptor, the
headꢀtoꢀtail arrangement is broken, leading to the generation of noncentrosymmetric space groups
Pna21. In other words, without the Jꢀaggregation of organic chromophores, the solid is still SHG
active, in which the cyano group controls the segregation of (CEMAS)+ NLOꢀphore layer. The
large SHG of 5 stems from this macroscopic polarity.
Optical diffuseꢀreflection spectra
The phase purities of crystals of 1−5 for physical property measurements have been verified
by powder Xꢀray diffraction (PXRD) (Fig. S8). The experimental PXRD patterns are in good
agreement with the simulated patterns from the singleꢀcrystal structures, suggesting the good
phase purities of the bulk crystalline materials. Solidꢀstate unpolarized visible/nearꢀIR absorption
spectra of 1ꢀ5 and their corresponding organic chromophores with the thickness of 0.6−0.8 mm
were recorded from powder samples at room temperature (Fig. 5a). Organic chromophores and
their hybrids 1ꢀ5 exhibit broad adsorption zones from ultraꢀviolet (260–600 nm) to nearꢀinfrared
(650ꢀ800nm) and IR. The optical diffuseꢀreflection spectra of hybrids 1ꢀ5 (imaginary line) are
generally the same with their corresponding organic chromophores (solid line), suggesting that the
optical adsorptions stem from the organic chromophores (from 270 to 650 nm centered at about
440 nm). 35,55,56 Among them, (DPAS)·I and
3 illustrate the narrowest adsorption, and due to the
presence of larger conjugated moiety naphthalene in (DMAQS)·I and 2, the widest adsorption
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zone can be found. Bathochromic shifts about 35ꢀ60nm of hybrids 1ꢀ5 compared with their
corresponding organic chromophores can be obtained, which should be attributed to the lower
polarity in the hybrids because the organic functional molecules are highly sensitive to the polarity
of the environment.57,58 In addition, no obvious narrow absorption bands are observed for 1ꢀ4, so
organic chromophores do not tend to form Jꢀaggregates in the hybrids because of the hindrance of
iodoargentates. Specially, the adsorptions in nearꢀinfrared zone (650ꢀ800nm) might also originate
from the chargeꢀtransfer between iodoargentates and organic chromophores.8 Such a charge
transfer between organic molecules and inorganic metal halides has already been reported.39 All
samples are transparent among 900ꢀ2100 nm with weak absorptions around 1700 and 1950 nm,
which might be assigned to the overtones of the C−H stretching vibrations. 8
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Solidꢀstate UV–Vis diffuse spectra of 1ꢀ5 calculated from the diffuse reflectance data by
using the Kubelka–Munk function is plotted in Fig. 5b. The band gaps can be estimated as 1.67,
1.42, 1.91, 1.75 and 1.60 eV for 1–5 respectively, indicating that all compounds are
semiꢀconductors with narrow gaps. These gaps are greatly lower than other iodoargentateꢀbased
hybrids (for example, 2.95 eV in (Etbtz)(AgI2)), 3 which might be explained as the introduction of
large πꢀconjugated organic chromophores. It’s universally accepted that the band gaps increase as
the dimensionality decreases. 39 Therefore, the gaps of five compounds exhibit obvious blue shifts
compared with the measured value of 2.75 eV for bulk AgI. The optical gap of
3 (1.91 eV) and 4
(1.75 eV) are obviously higher than others, which might be assigned to the hindrance of larger
groups (phenyl) to inhibit the organicꢀinorganic chargeꢀtransfers. According to literature, a high M
(M = Cu or Ag) content will lead to the low electronic band gap.59 So the slight blue shift of the
band gap of 4 compared to that of 3 can be ascribed to its relatively higher Ag/I ratio.
Photoluminescent emissions and secondꢀorder nonꢀlinear optical property
Oneꢀphoton photoluminescence spectra of 1, 3, 4, 5 and their organic chromophores
measured at room temperature in the solid state are shown in Fig. 6. And
compared with (DMAQS)·I (emissions at 678, 778nm). Upon excitation, broad red emissions at
662, 731nm (for (DAST)·I and ), 625, 661 nm (for (DPAS)·I and ), 675, 716 nm (for (DPTAS)·I
and ), 695, 701 nm (for (CEMAS)·I and ) can be detected (exited, emission peaks and redꢀshift
2 shows no luminescence
1
3
4
5
are summarized in Table 3). The luminescence of iodoargentates were commonly observed at
about 450ꢀ500nm,51 So the intense luminescence in this work all stem from the organic
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chromophores. Upon comparison the emissions of organic chromophores and their hybrids,
enhanced and slightly redꢀshifted emissions can be observed, which have been documented in
other NꢀArylstilbazolium organic nonlinear optical chromophores and their metal complexes.37
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Among them,
1 exhibits the largest enhanced amount (two times augment) and redꢀshift (69nm).
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The luminescence quenching in the solid state of πꢀdelocalized moleculesꢀcontaining systems has
been explained as the intermolecular interactions such as π···π stacking.60 In
2
, strong π···π
stacking interactions with centroidal distance of 3.548(5) Å, which may leads to the mixing of
HOMO and LUMO orbitals of π system, and consequently, produces excited states with low
reduced efficiency.60 But strong π···π stacking interaction is also present in
quenching process didn’t take place. This might be ascribed to the strong Hꢀbond with
iodoargentate and worse overlap of two planes compared with that in
Herein, considered that crystallizes in noncentrosymmetric (NCS) space group Pna21, its
secondꢀorder nonꢀlinear optical effect was investigated. The experimental SHG intensities under
2.0 um radiation as a function of particle sizes for crystalline is given in Fig. 7. As shown by Fig.
5, the emission
2
.
5
5
7, the SHG intensities of
5 increases with particle sizes and approach almost saturated, indicating
its phasematchable property of Type I.61 In addition, SHG intensity of
5
is equal to that of KDP
with the same particle size of 300−350 ꢁm (Fig. 7). The SHG result reveals that the combination
of Nꢀarylstilbazolium organic nonlinear optical chromophores with iodoargentates can generate a
favorable NCS packing and excellent optical secondꢀorder nonlinearity. It is universally accepted
that the SHG behavior is determined by the size and the orientation of the dipole moments of the
SHG active units in the NCS structure. To make clear the SHG resource of 5, the magnitude and
direction of the dipole moments of the Ag5I94ꢀ building block (constructed from Ag4I4 cubane and
2+
bridged AgI4 tetrahedron) and (CEMAS)2 pair in the asymmetric unit were calculated using a
4ꢀ
G09 program (Table S5). The dipole moment of the Ag5I9 unit is 6.5147 D, while that of
2+
(CEMAS)2 pair is relative small with amount of 2.6685 D (the dipole moment of a water
molecular is known as 2.16 D). Thus the direction of the net dipole moment of a unit cell of
5
4ꢀ
mainly derives from the polarizations of the asymmetric contribution of Ag5I9 unit mixing with
smaller contributions from CEMAS+ chromophore. The SHG behavior can also be achieved
without the Jꢀaggregates of organic chromophores. In 5, the introduction of cyano group results in
2+
the unꢀsymmetric (CEMAS)2 pair, and consequently, in the polarizations of iodoargentate. It’s
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worth noting that the spatial arrangements of the SHGꢀactive units (Ag5I9)4ꢀ and (CEMAS)22+ pair
are not in complete alignment, which inhibits the theoretical enhancement of macroscopic
polarizabilities. Therefore, a higher SHG response can be expected if the dipole moments of
SHGꢀactive units are aligned more effectively in a new NCS hybrid. How to control the
aggregations of organic chromophore via crystal engineering method to improve its NLO property
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is still a big challenge.
Electronic Structure Calculations
In order to look further insight into the linear optical properties of 1−5, DFT calculations
illustrated by band structures along with high symmetry points of the first Brillouin zone and
density of states (DOS) were executed using the CASTEP code in Materials Studio 8.0. The band
structures, total and partial DOS of 1−5 along certain symmetry directions are given in Fig. 8, Fig.
S9 and Fig. S10, respectively. The calculated band gaps of 1−5 using the GGAꢀPBE are 1.43, 1.05,
1.49, 1.22 and 1.38 eV, which are slightly smaller than their corresponding experimental values of
1.67, 1.42, 1.91, 1.75 and 1.60 eV, respectively. But the trend is right with largest gap observed in
3
and lowest one in
2
. This discrepancy is contributed to the band gap underestimation of DFT
method.62 Besides,
1
and exhibit indirect band gaps, but 3, 4, 5 are direct band gaps. The bands
2
can be explained by PDOS (Fig. 8, Fig. S10). As shown by the total and partial DOS diagrams,
1−5 possess similar electronic structures, in which the contributions of organic chromophores are
dominated mixing by iodoargentates in the frontier orbitals. In detail, the top of the VBs between
−5 and Fermi energy originate from the π bonding orbitials of organic chromophores mixed with
small amount of Agꢀ4d, Iꢀ5p states. And the bottom of the CBs are almost the contribution of the
p−π* antibonding orbitals of organic chromophores. So both HOMO and LUMO of crystal
orbitals in this work are the components of organic chromophores. These orbital components
support the fluorescence assignments that the intense luminescences of four compounds all stem
from the organic chromophores, i. e., the emissions are the transitions from HOMO (π bonding
orbitials) to LUMO (p−π* antibonding orbitals) of organic chromophores. In the band structure of
βꢀAgI, its CBs stem form Agꢀ5s, Iꢀ5p orbitals. So conclusion could be drawn that organic
chromophores adopt a direct way to modify the band gaps of iodoargentate hybrids, which have
been reported in other metal halideꢀbased hybrids containing aromatic organic molecules.48,63
Consequently, the intrinsic absorption of 1−5 can be mainly ascribed to the π−π* transfer of
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charge organic chromophores assisted by transitions from Iꢀ5p state to p−π* orbitals of the organic
chromophores.
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CONCLUSIONS
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In summary, combination of Nꢀarylstilbazolium organic nonlinear optical chromophores with
iodoargentates results in series of new hybrids, whose single crystals were grown from solutions
or solvothermal methods. The stilbazoliums vary from their electron donating ꢀNR2 substituents, i.
e. R=ꢀMe, ꢀPh, pꢀCH3ꢀPh, ꢀCH2CH2CN, among which ꢀCH2CH2CN containing hybrid
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[(CEMAS)2(Ag5I7)]n (
[(DAST)(Ag2I3)]n ( ), [(DMAQS)(Ag2I3)]n (
are centrosymmetric structures. The (Ag5I7)n chain in
5
, space group Pna21) is noncentrosymmetrical, however, other four hybrids
), [(DPAS)(Ag2I3)]n ( ), [(DPTAS)2(Ag5I7)]n (
are new kinds of condensation
1
2
3
4)
2nꢀ
4
and 5
modes in hybrid iodoargentates. UV/Vis/nearꢀIR adsorptions and nearꢀIR photoluminescences
have been observed. All the organic chromophores are stacked as headꢀtoꢀtail arrangements,
resulting in second harmonic generation (SHG) inactive in 1ꢀ4. But 5 is SHG active without
Jꢀaggregation of organic chromophore, whose symmetry break was driven by the formation of
hydrogen bonds around cyano group. This work provides a theoretical guide for the design of new
NLO materials.
ASSOCIATED CONTENT
Supporting Information The Supporting Information including the selected bond lengths and
1
angles, hydrogen bond details,
π–
π
stacking interactions, H NMR and 13C NMR spectra, the
photographs of asꢀgrown crystals, additional structural figures, PXRD patterns, band structures
and PDOS are available free of charge on the ACS Publications website.
Accession Codes CCDC 1567096 (for
1), 1582739 (for 2), 1583256 (for 3), 1582759 (for 4),
1582820 (for ) contain the supplementary crystallographic data for this paper. These data can be
5
obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The CambridgeCrystallographic Data Centre, 12
Union Road, Cambridge CB21EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: lihh@fzu.edu.cn and zrchen@fzu.edu.cn.
ORCID
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HaoꢀHong Li: 0000ꢀ0003ꢀ3543ꢀ7715
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Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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We acknowledge support of this research by National Natural Science Foundation of China
(NOS: 21771038) and National Natural Science Foundation of Fujian Province (2018J01684,
2017J01409).
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Table 1. Summary of the crystal data and structure determination
Compound
1
2
3
4
5
Empirical formula
C16H19N2Ag2I3
835.77
Monoclinic
P21/c
C20H21N2Ag2I3
885.83
C26H26N2Ag2I3
959.90
C56H54N4 Ag5I7
2210.68
Monoclinic
P2/n
C36H40Ag5I7N6
1984.39
Orthorhombic
Pna21
Formula mass
Crystal system
Triclinic
Pꢀ1
Triclinic
Pꢀ1
Space group
a[Å]
b[Å]
c [Å]
α[º]
18.92 (1)
15.679 (8)
7.237 (4)
90.00
8.203 (3)
11.936 (4)
13.473 (4)
110.823 (4)°
90.663 (5)°
106.013 (5)°
1176.3 (7)
2
8.3233 (9)
10.2502 (9)
16.8379 (16)
105.111 (2)°
90.701 (2)°
90.708 (2)°
1386.6 (2)
2
20.836 (4)
6.6692 (11)
22.920 (4)
90.00
14.3136 (12)
15.5748 (13)
22.2132 (19)
90.00
β[º]
95.993 (8)
90.00
103.374 (2)
90.00
90.00
γ[º]
90.00
V[Å]
Z
2135(2)
4
3098.6 (10)
2
4952.0 (7)
4
Dc[g/cm3]
2.600
2.501
2.299
2.369
2.662
ꢀ[mm－
]
6.172
5.610
4.769
5.078
6.338
1
F(000)
1528
816
892
2048
3616
Reflections, total
7040
6068
8056
9937
18153
Reflections, unique
3671
3412
4668
5293
6191
(Rint=0.0237)
3086
(Rint= 0.0168)
4174
(Rint=0.0306)
3729
(Rint=0.0276)
5704
(Rint= 0.0297)
Reflections, observed
Goodnessꢀofꢀfit on F2/ 1.082
2991
1.021
1.047
1.035
1.054 / 0.05(5)
Flack factor
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No. of parameters refined 211
247
299
329
491
R1[I>2σ(I)]a
0.0484
0.0377
0.0918
1.501, −1.504
2 2
0.033
0.0611
0.0476
0.1574
wR2 [I>2σ(I)]
0.0829
2.296, −1.522
0.1517
0.1272
Residual extremes(e/Å3)
1.249, −1.669
1.808, −2.120
4.460, −2.887
a R1=∑||F0| ꢀ |Fc||/∑|F0|, wR2={∑[w(F0 ꢀFc2)2]/∑[w(F0 ) ]}1/2
.
2
Table 2 Structural parameters of organic chromophores in solids and in gas
Dihedral angle Sum of C–N–C Sum of C–N–C Bond length of Torsion angle (°)
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17
18
19
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35
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Organic
chromophores
between
pyridine
angles
around angles
around ethenyl double
and pyridine N (°)
amido N(°)
bond (Å)
benzene rings (°)
DAST+ in 1
11.13
10.93
1.78
360.0(3)
359.9(9)
360.2(0)
360.0(0)
360.1(6)
359.9(7)
360.2(4)
358.0(0)
359.0(3)
358.9(3)
358.0(8)
357.9(3)
360.0(2)
360.0(0)
358.7(2)
358.4(9)
1.302(17)
1.3005(2)
1.333(10)
1.3333(9)
1.337(8)
178.9(6)
178.9(6)
177.6(8)
177.6(9)
175.1(4)
175.1(4)
177.4(3)
177.4(2)
Free DAST+
DMAQS+ in 2
Free DMAQS+
DPAS+ in 3
Free DPAS+
DPTAS+ in 4
Free DPTAS+
CEMAS+ in 5
Free CEMAS+
1.77
8.12
7.89
1.3364(1)
1.339(14)
1.3382(2)
9.05
9.02
6.87/13.28
5.99
360.7(0)/359.8(3) 359.9(1)/358.7(3) 1.31(3)/ 1.30(2) 177.9(0)/178.5(8)
360.0(0) 359.9(9) 1.311(5) 177.9(0)
Table 3 The excited and emission peaks for hybrids and their organic chromophores
Compound
Excited peaks (nm)
Emission maxima (nm)
Amount of redꢀshift (nm)
344
428
300
438
352
441
430
434
662
731
625
661
675
716
695
701
69
(DAST)·I
1
36
41
6
(DPAS)·I
3
(DPTAS)·I
4
(CEMAS)·I
5
Ag2I6 unit
(a)
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(b)
(c)
Fig. 1 (a) Structure of (Ag2I3)nnꢀ chain constructed from edgeꢀsharing Ag2I6 unit; (b) Structure of DAST+; (c)
Packing diagram with inorganic locating in the cavities defined by headꢀtoꢀtail arranged organic
chromophores in 1
Ag4I8 unit
(a)
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(b)
Fig. 2 (a) 1ꢀD (Ag2I3)nnꢀ chain built from edgeꢀsharing Ag4I8 unit; (b) π–π stacking interactions between
headꢀtoꢀtail arranged (DMAQS)+ cations in 2
(a)
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(b)
(c)
Fig. 3 (a) Structure of Ag5I10 unit; (b) Structure of (Ag5I7)n2nꢀ chain; (c) Packing diagram showing CꢀH···I
hydrogen bonds of 4
(a)
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(b)
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Fig. 4 (a) Structure of (Ag5I7)n2nꢀ zigzagꢀlike chain built from cubaneꢀlike Ag4I4 nodes and AgI4 tetrahedron;
(b)Structure of unꢀsymmetric (CEMAS)2n2n+ chain based on CꢀH···N hydrogen bonds showing π–π stacking
interactions; (c) Packing diagram of 5 showing the hydrogen bonds in 5
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Fig. 5 (a) Solid state electronic spectra of 1ꢀ5 and their organic chromophores; (b) optical diffuse reflectance
spectra for 1ꢀ5
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