An insight into the controllable synthesis of Cd(ii) complexes with a new multifunctional ligand and its application in dye-sensitized solar cells and luminescence properties

Article abstract of DOI:10.1039/c4ta06671e

Based on a new design of 4-cyanobenzyl-based 1,2,4-triazole ligand 4-(1,2,4-triazolylmethyl) cyanobenzene (TMCB), a series of cadmium complexes 1-5′ from a mononuclear to three-dimensional (3D) structure have been synthesized through hydro(solvo)thermal reactions; they were generally formulated as [Cd(TMCBA)₂]_n (1), [Cd(TMCB)(1,4-bda)(H₂O)]_n (2), {[Cd₂(TMCB)₄(1,4-bda)₂(H₂O)₂]_n·3H₂O}_n (3), {[Cd(TMCB)₄(H₂O)₂]·(NO₃)₂·(H₂O)₂}_n (4), [Cd_1.5(1,4-bda)_1.5(DMF)₂]_2n (5) and [Cd_1.5(1,4-bda)_1.5(DMF)₂]_2n (5′) (TMCBA = 4-(1,2,4-triazolylmethyl) benzoic acid, which is formed from the hydrolysis of TMCB; 1,4-H₂bda = 1,4-benzenedicarboxylic acid; the difference between two genuine supramolecular isomers of 5 and 5′ is the use of TMCB as the additive agent for the reaction). Complexes 1-5′ exhibit tunable luminescence with emission maxima containing deep blue, blue, light blue, green and deep green region at 298 K or 77 K in both different solvents (polarity: DMSO > CH₃OH > CHCl₃) and solid state. Interestingly, the good thermal stability accompanied by their compensated adsorption to ruthenium complex N719 in the region of low wavelength, enabled 1 and 4 to serve as co-sensitizers in combination with N719 in dye sensitized solar cells (DSSCs). After co-sensitization with N719, the overall conversion efficiency of 1 and 4 were found to be 7.68% and 6.85%, which are 40.40% and 25.23% higher than that for DSSCs only sensitized by N719 (5.47%) under the same conditions, respectively. The improvement in efficiency is attributed to the fact that complexes 1 and 4 overcome the deficiency of N719 absorption in the low wavelength region of ultraviolet and blue-violet, offset competitive visible light absorption of I₃^- and reduce charge recombination due to the formation of an effective cover layer of the dye molecules on the TiO₂ surface. As a result, the synthesized complexes are promising candidates as co-adsorbents and co-sensitizers for highly efficient DSSCs.

Full text of DOI:10.1039/c4ta06671e

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Application in dye–sensitized solar cells and luminescence properties: an insight
into the controllable synthesis of Cd(II) complexes with the new multifunctional
ligand
Song Gao,a Rui Qing Fan,*,a Xin Ming Wang,a Liang Sheng Qiang,a Li Guo Wei,a Ping Wang,a Hui Jie Zhang,a
Yu Lin Yang*,a, Yu Lei Wangb
5
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
Based on a new design of 4-cyanobenzyl–based 1,2,4-triazole ligand 4-(1,2,4-triazolylmethyl)
10 cyanobenzene (TMCB), a series cadmium complexes 1–5’ from mononuclear to three–dimensional (3D)
structure have been synthesized through hydro(solvo)thermal reactions, generally formulated as
[Cd(TMCBA)2]n (1), [Cd(TMCB)(1,4-bda)(H2O)]n (2), {[Cd2(TMCB)4(1,4-bda)2(H2O)2]n·3H2O}n (3),
{[Cd(TMCB)4(H2O)2]·(NO3)2·(H2O)2}n (4), [Cd1.5(1,4-bda)1.5(DMF)2]2n (5) and [Cd1.5(1,4-
bda)1.5(DMF)2]2n (5’) (TMCBA = 4-(1,2,4-triazolylmethyl) benzoic acid, which is formed from the
15 hydrolysis of TMCB; 1,4-H2bda = 1,4-benzenedicarboxylic acid; the difference between two genuine
supramolecular isomers of 5 and 5’ is to use TMCB as additive agent for the reaction). Complexes 1–5’
exhibit tunable luminescence with emission maxima containing deep blue, blue, light blue, green and
deep green at 298 K or 77 K both in different solvents (polarity: DMSO > CH3OH > CHCl3) and in the
solid state. Fascinatingly more, the good thermal stability accompanied by their compensated adsorption
20 to ruthenium complex N719 in the region of low wavelength, enabled 1 and 4 serve as co-sensitizers in
combination with N719 in dye sensitized solar cells (DSSCs), respectively. After co-sensitization with
N719, the overall conversion efficiency of 1 and 4 can achieve 7.68% and 6.85%, which are 40.40% and
25.23% higher than that for DSSCs only sensitized by N719 (5.47%) under the same conditions,
respectively. The improvement in efficiency is attributed to the fact that complexes 1 and 4 overcome the
25 deficiency of N719 absorption in the low wavelength region of ultraviolet and blue-violet, offset
competitive visible light absorption of I3- and reduce charge recombination due to formation of an
effective cover layer of the dye molecules on the TiO2 surface. As a result, the synthesized complexes are
promising candidates as co-adsorbents and co-sensitizers for highly efficient DSSCs.
45
As a typical representative of luminescent materials, Cd(II)-
Introduction
based MCCs have gained intensive attention mainly due to three
aspects: (i) Cd(II) is lower-cost and easy to get for application. (ii)
Cd(II) has a versatile mode of coordination (coordination number
4-8), which can lead to fascinating topological structures.14 (iii)
30 The luminescent properties of metal coordination complexes
(MCCs) have attracted ever growing attention in recent years.1-4
These luminescence MCCs possess wider applications such as
solvent sensor device,5 smart windows,6 ophthalmic lenses,7
optical filters and optical memory,8,9 etc. However, exploration of
35 these luminescent behaviors is still a big challenge which could be
influenced by complex thermal stability, photostability, solubility
and other factors. The key to design luminescent materials is the
matching of organic ligand and central metal ion which can
provide the platforms to generate ultraviolet absorption and
40 luminescence.10-13
50 The presence of electronically saturated d10-metal Cd(II) ion is
appropriate because it imposes conformational rigidity to the
ligand and prevents energy loss via bond vibration and electron
transfer processes, whereas paramagnetic transition metals quench
fluorescence by different electron/energy transfer mechanisms.15
55 The enormous variability of available ligand–metal combinations
opens the possibility of creating luminescence “by design”. Up to
now, complexes containing 1,2,4-triazole ligand and its derivatives
have been widely studied in the construction of illuminant
MCCs,16-22 which have strong absorption in the ultraviolet and
a Department of Chemistry, Harbin Institute of Technology, Harbin, 150001 (P.
R. China). E-mail: fanruiqing@hit.edu.cn (R. Q. Fan); ylyang@hit.edu.cn (Y.
L. Yang)
region.23,24
However,
the
4-(1,2,4-
b National Key Laboratory of Science and Technology on Tunable Laser,
Harbin Institute of Technology, Harbin, 150025 (P. R. China)
† Electronic supplementary information (ESI) available: Experimental details
and results of luminescence experiments. The CIF files give crystallographic
data for complexes 1–5’. Fig. S1–S24, Scheme S1, Scheme S2 and Tables S1–
S4. CCDC 1028900, 1028901, 1028902, 1028903, 1028904 and 1028905. For
ESI and crystallographic data in CIF or other electronic format see DOI:
10.1039/b000000x
60 blue-violet
triazolylmethyl)cyanobenzene (TMCB) (Scheme 1) and 4-(1,2,4-
triazolylmethyl)benzoic acid (TMCBA) (through controlling the
reaction conditions, TMCBA was produced from the cyanophoric
hydrolytic reaction of TMCB) as representatively flexible ligands,
65 are never investigated in this field. These flexible ligands TMCB
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and TMCBA with π-conjugated system play crucial roles in 1 and 4 could compensate for that of N719 in the low wavelength
determining the structure and luminescent properties of the region of ultraviolet and blue-violet and the light harvesting was
complexes because of the diversiform coordination mode and the enhanced, which lead to 40.40% and 25.23% improvement of
flexible nature of –CH2– spacers.
DSSCs performance than blank N719. Our research breaks
40 through the low utilization problem of N719 absorption efficiency
in ultraviolet and blue-violet region. Consequently, the excellent
properties indicate the great potential of the MCCs being utilized
as the multifunctional material in both luminescence and DSSCs
fields.
5
45
Results and Discussion
Synthesis: We have successfully obtained six new Cd(II)
complexes from 0D to 3D, the reaction routes of 1–5’ are
shown in Scheme 2. (1) 4→3:. The only N atom from 1,2,4–
triazole displays the monodentate mode to connect metal center
Cd results in forming the monomer structure of 4. The effect of
aromatic polycarboxylate coligands with different constructions,
and multifarious coordination modes on the resultant different
structures and topologies cannot be neglected. In order to
design and synthesis of high dimensional complexes, The
aromatic polycarboxylate auxiliary ligands are key factors to
control the connectivity of multidimensional net because they
have more coordination sites.33 Therefore, based on the
synthetic procedure of 4, we introduced auxiliary ligand 1,4–
H2bda and obtained 1D structure of 3. (2) 3→2: complexes 2
and 3 were prepared using the same reactants but with different
molar ratios (Cd(NO3)2·4H2O / TMCB / 1,4–H2bda ligand ratio
is 2:1:1 for complex 2 and 1:1:1 for complex 3. It is proven that
higher metal–ligand ratio is apt to permit to construct of high
dimension architectures.34 (3) 2→1: Unexpectedly, when the
NaOH was added in the reaction system, the resultant structures
of the complexes altered subsequently.35 In alkaline conditions,
the cyangroup of TMCB undergoes hydrolysis to generate the
TMCBA. Not only the nitrogen atom in the 1,2,4–triazole but
also the oxygen atoms of carboxylic acid can participate in the
coordination, and formed 3D structure, consequently no
participation of 1,4–H2bda ligand. (4) 5→5’ (effect of TMCB
Scheme 1 Synthetic procedure of TMCB ligand.
10
As the rapid development of energy conversion devices, the
MCCs with specific optical property are being applied in the dye
sensitized solar cells (DSSCs) gradually.25 In the photoelectric
transformation, co-sensitization by means of multiple sensitizers
including MCCs would appear to be more effective to improve the
50
55
60
65
70
15 absorption ability of solar cell.26 MCCs as co-sensitizer or co-
adsorbent in DSSCs could not only compensate the absorption
−
−
spectra but also overcome the competitive light absorption by I /I3 ,
avoid dye aggregation and reduce charge recombination, which
will lead to enhanced DSSCs performance by co-sensitization.27,28
20 Among numerous of MCCs, noble metal (Ir, Ru, Pd)29-32 MCCs
are introduced to DSSCs system as co-sensitizers. Although the
noble metal MCCs show good photoelectric conversion
performance, the expensive price hinders their practical application.
The efforts for increasing solar cell efficiency with a low
25 production cost have been the primary objective of solar energy
conversion. For this reason, our group synthesized low-cost Cd(II)
metal complexes, in order to replace precious metal complexes as
co-sensitizers.
In this paper, the sensitive luminescence is realized by the
30 rational design and controllable construction of six Cd(II)
complexes from mononuclear to 3D network based on flexible
ligand TMCB or TMCBA. Since the strong absorption in 320–378
nm and excellent stability, complexes 1 and 4 are selected to be co-
sensitizers and applied in the DSSC system sensitized by N719,
35 respectively. It is showed that the absorption spectra of complexes
75
80
85
Scheme 2 Reaction routes of complexes 1–5’.
2
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liangd act as additive agents): 5 and 5’ are genuine supramolecular
isomers having identical chemical compositions for not only the
coordination network but also the whole crystal. So, the formation
of supramolecular isomers in this system is dominated by whether
the TMCB ligand is used as an additive agent in the reaction.36-38
In fact, the isomerism arising from the TMCB ligand is
fortuitously observed since the additive is not incorporated in the
final crystalline product of 5’. This fact intensively indicates that
TMCB molecules may ingeniously influence the micro–
60
5
10 environment of the reaction system, generating different
superstructures from those crystallized in the absence of TMCB
molecules.
65
Structure Description: {[Cd(TMCBA)2]}n (1). Single–crystal
15 X–ray diffraction analysis of complex 1 reveals that it contains one
Cd2+ cation and two crystallographically independent TMCBA–
anions in the asymmetric unit (Fig. S1a). In 1, the metal center
Cd1 is six–coordinated, forming a slightly distorted octahedron
with [CdO4N2] coordination mode (Fig. S1b). The two carboxylate
20 groups from the TMCBA– anion provide four bidentate
70
1
1
Fig.
2
(a) Polyhedral and ball–and–stick representation of the 3D
coordination mode μ2–ηO :ηO donor oxygen atoms (O1, O2, O1A
and O2A) (Scheme S1), and the two triazole rings provide two
nitrogen atoms (N1, N1A), respectively. Two adjacent cadmium
ions are connected through O1, O2, O1A and O2A atoms deriving
25 from two TMCBA– anions, giving rise to an infinite 1D linear
chain along the b axis (Fig. 1a). Along the crystallographic c axis,
Cd(II) ions are connected by two TMCBA– ligands (Fig. 1b) to
form a 1D “wave–like” chain in which all the metal atoms are
coplanar. Two adjacent 1D chains are interconnected to form the
30 2D layer (Fig. 1c). These 2D layers are further connected into a 3D
chair–shaped framework structure (Fig. 2a). In order to simplify
the intricate structure of 1, the secondary building unit (SBUs)
[CdO4N2] unit can be considered as a 6–connected node, and
TMCBA– anions could be considered as a 3-connected node (Fig.
35 2b). The framework exhibits octatomic ring chair–shaped cavity
with a size of ca. 20.473 × 10.236 Å (Fig. 2c) according to the
Cd1···Cd1 distances. Therefore, the 3D framework of 1 can be
described as a rare octatomic ring chair–shaped (3,6)-connected
network (Fig. 2d).
framework structure in 1. (b) Blue ball representation of TMCBA– anion;
(c) The detail of the cavities in 1. (d) Schematic representation of the
octatomic ring chair–shaped 3D (3,6)-connected topology in the complex 1.
75
[Cd(TMCB)(1,4–bda)(H2O)]n (2). The asymmetric unit of
complex 2 consists of one crystallographically independent Cd2+
cations, two TMCB ligands, one 1,4–bda2– anion, and one
coordinated water molecule (Fig. S2a). Every Cd2+ cation is seven
coordinated with slightly distorted pentagonal bipyramid
80 coordination geometry [CdO5N2] by four O atoms (O1, O2, O4
and O5) from 1,4–bda2– adopting bidentate-chelate µ2= η1:η1:η1:η1
bridging fashion (Scheme S2), one O3 from one coordination
water molecule, and two nitrogen atoms (N1 and N2) from TMCB
ligand (Fig. S2b). The adjacent cadmium ions are interconnected
85 through O1, O2, O4 and O5 atoms along the a axis, formed an
infinite 1D “wave–like” chain (Fig. 3a). Each TMCB ligand links
two adjacent cadmium ions with two triazole group nitrogen atoms
to form a 1D linear chain structure along the b axis (Fig. 3b). Two
adjacent chains are interconnected to construct a 2D grid layer (Fig.
90 3c). From the topological point of view, the Cd2+ could be
considered as the node, TMCB and 1,4–H2bda ligands as the
linkers. Thus, the 2D framework of 2 can be described as a 4–
connected 44 net (Fig. S3a). The 3D architecture of 2 is reinforced
by the intermolecular hydrogen bonds interaction from O3-
95 H3B···N4 and O3-H3C···O5 (Fig. S3b).
40
45
{[Cd2(TMCB)4(1,4–bda)2(H2O)2]n·3H2O}n (3). It contains
two Cd2+ cations, four TMCB ligands, two 1,4–bda2– anions,
two coordination water molecules and three free water
100 molecules in the asymmetric unit of complex 3 (Fig. S4a). Two
Cd2+ cations exhibit identical slightly distorted pentagonal
bipyramid coordination environments (Fig. S4b). Two 1,4–
bda2– anions display the bidentate-chelate µ2= η1:η1:η1:η1 mode
to connect center metal (Scheme S2). Each Cd2+ cation linked
with two TMCB ligands into a dimer which is further bridged
by 1,4–bda2– anion to form an infinite 1D chain structure (Fig.
4a). Moreover, the chains are linked through O1W-H1WC···O8
hydrogen bonding interactions giving rise to layer (Fig. 4b).
50
Fig. 1 (a) Polyhedral and ball–and–stick representation of the 1D chain105
55 structure along b axis in 1. (b) Polyhedral and ball–and–stick representation
of the 1D “wave-like” chain along c axis. (c) Polyhedral and ball–and–stick
representation of the 2D layer in 1, hydrogen atoms are omitted for clarity.
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These layers structure are further stabilized by π−π stacking asymmetric unit (Fig. S5a). The Cd1 center adopts a distorted
interactions (3.534 Å) between the benzene rings of the two octahedral geometry, with four nitrogen atoms from TMCB and
TMCB ligands (Fig. 4c), forming
framework (Fig. 4d).
a
3D supramolecular 60 two oxygen atoms from coordinated water molecules (Fig.
S5b). Each Cd2+ cation links four TMCB ligands and two
coordinated water molecules to form a mononuclear structure
(Fig. 5a). What’s more, the triazole ring and benzene ring of
each one TMCB ligand are not coplanar. This conformation is
65 further stabilized by intramolecular/intermolecular O–H···O
hydrogen bonding, and generated a 3D structure of complex 4
(Fig. 5b).
5
10
15
20
25
70
75
30 Fig. 3 (a) Polyhedral and ball–and–stick representation of the 1D “wave–
like” chain structure along a axis in 2. (b) Polyhedral and ball–and–stick
representation of the 1D linear chain structure along b axis in 2. (c)
Polyhedral and ball–and–stick representation of the 2D layer in
2
(hydrogen atoms are omitted for clarity).
35
40
45
80
Fig. 5 (a) The illustration of mononuclear structure in 4 (nitrate ions, water
molecules and hydrogen atoms are omitted for clarity). (b) The 3D
supramolecular structure in 4 (hydrogen bonds are shown by black dots).
[Cd1.5(1,4–bda)1.5(DMF)2]2n (5). The crystal structure
85 determination reveals that complex
5
contains three
crystallographically unique Cd2+ cations, three 1,4–bda2– anions,
and four DMF molecules, among them, Cd3, Cd4 cations occupies
half position (Fig. S6a). Three Cd cations display distorted [CdO6]
octahedral geometry (Fig. S6b). The central Cd3/Cd4 cation is
90 linked to two symmetry–related terminal Cd2 and Cd2A (Cd1 and
Cd1A) cations by six carboxylate groups of 1,4–bda2– anions in
1
2
1
2
1
1
1
1
μ4–ηO :ηO :ηO :ηO and μ4–ηO :ηO :ηO :ηO coordination modes
Fig. 4 (a) Polyhedral and ball–and–stick representation of the 1D chain (Scheme S2) to afford a Cdoct–Cdoct–Cdoct SBUs with Cd3Cd2
50 structure in 3 (water molecules and hydrogen atoms are omitted for clarity).
(b) The hydrogen bonding interactions between the molecules and (c)
packing structure for 3. (d) A 3D supramolecular structure of 3 (hydrogen
bonding is turquoise dashed line).
(Cd3Cd2A) distance of 3.661(10)
Å
and Cd4Cd1
95 (Cd4Cd1A) distance of 3.663 (10) Å. Through O9, O9A, O10
and O10A atoms of 1,4–bda2– anion, the linear trinuclear units
(Cd1oct–Cd4oct–Cd1Aoct) are interconnected to form an infinite 1D
“zigzag–like” chain (Fig. 6a). Another “zigzag–like” chain
composed of the linear trinuclear units (Cd2oct–Cd3oct–Cd2Aoct) is
connected with O11, O11A, O12 and O12A atoms originating
from the other 1,4–bda2– anion. Furthermore, the two “zigzag–
like” chain are further connected by the rest of two 1,4–bda2–
{[Cd(TMCB)4(H2O)2]·(NO3)2·(H2O)2}n (4). Complex
4
55 consists of one Cd2+ cation, four crystallographically
independent TMCB ligands, two coordinated water molecules,100
two free water molecules and two free nitrate ions in the
4
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anions to generate the 2D layer structure. Interestingly, in this 2D
structure, each central linear trinuclear unit is connected with
surrounding six linear trinuclear units through three 1,4–bda2–
anions (Fig. 6b). Notably, in a single six membered rings has a
channel, which allows the other two identical six membered rings 60
to penetrate, affords a threefold interpenetrating architecture (Fig.
6c).
5
65
10
15
20
70
Fig. 7 (a) The 1D “wave–like” chain of complex 5’ (DMF molecules, water
molecules and hydrogen atoms are omitted for clarity). (b) The illustration of 2D
75 layer in 5 along a axis. (c) A twofold interpenetration 2D honeycomb 3-
connected layer of 5’ along c axis.
From a topological perspective, the whole framework of 5’
can be topologically represented as twofold interpenetration 2D
honeycomb 3-connected network (Fig. S9a), which are further
80 stacked up by intermolecular forces to complete the final 3D
structure (Fig. S9b).
To check the phase purity of the products, powder X–ray
diffraction (PXRD) experiments have been carried out for
complexes 1–5’ (Fig. S10). The peak positions of the
85 experimental and simulated PXRD patterns are in good
agreement with each other, indicating that the crystal structures
are truly representative of the bulk crystal products.39 The
differences in intensity may be owing to the preferred
orientation of the crystal samples. Variable–temperature X–ray
90 powder diffraction (VT–XRPD) patterns were obtained using a
Fig. 6 (a) The 1D “zigzag–like” chain of complex 5 (DMF molecules, water
25 molecules and hydrogen atoms are omitted for clarity). (b) The illustration of
single 2D layer in 5. (c) A threefold interpenetration 2D honeycomb 3-
connected layer of 5.
If the symmetrical trinuclear unit can be regarded as a 3–
connected node, connected with three 1,4–bda2– anions. In turn,
30 the 1,4–bda2– anions can be considered as linear bridges
between two nodes, the structure of 5 can reduced to a
threefold interpenetration 2D honeycomb 3-connected network
(Fig. S7a). It is worth noting that there are intermolecular
forces between the adjacent the 2D threefold interpenetration
35 layers to form a 3D structure (Fig. S7b).
PANalytical
X–ray
diffractometer,
equipped
with
monochromated Cu Kα radiation 40 mA, 40 kV. Each powder
pattern was recorded in the 5–50 °C range (2θ) from 50 °C to
700 °C with a step of 0.02° and a counting time of 0.4 s. The
95 temperature ramp between two consecutive temperatures was
10 °C/min (Fig. S11). The results confirm that for 1, no
framework change occurs before 250 °C. The diffraction
signature might reflect that the network starts to undergo a
phase transition from 300 to 400 °C, which induces the
100 structure collapse. After the structure destruction, only 10.9°
and 28.2° (2θ) peak is visible, which induces the structure
collapse to CdO. The X–ray thermodiffractogram of 1 is
[Cd1.5(1,4–bda)1.5(DMF)2]2n (5’). The supramolecular isomeric
2D network of 5’ was obtained under similar reaction conditions
without TMCB ligand as an additive agent. Structural analysis
indicates that asymmetric unit of 5’ consists of completely
40 identical components to those in 5 (Fig. S8a). In contrast to 5, the
terminal Cd1 and Cd1A cations exhibit [CdO7] distorted
pentagonal bipyramid geometry. The middle Cd2 cation displays
distorted octahedral geometry with [CdO6] (Fig. S8b). The three
1
2
1
1
1
2
1
2
1,4–bda2– anions with μ4–ηO :ηO :ηO :ηO and μ4–ηO :ηO :ηO :ηO
45 mode bind three Cd(II) centers (Scheme S2). Cd1 and Cd1A are
linked to Cd2 via carboxylate groups, forming a trinuclear Cdpenta
40-42
consistent well with the TG analyses.
–
Cdoct–Cdpenta SBUs. The carboxylate groups of the 1,4–bda2–
anions link the trinuclear SBUs into an infinite 1D “wave–like”
chain (Fig. 7a), which contains a Cd···Cd separation of 3.659(10)
50 Å. Such 1D “wave–like” chains are further interconnected by each
other, leading to the formation of a 2D layer structure along the a
axis (Fig. 7b). Notably, two 2D layers are interpenetrating with
each other to give a double–layered motif. It’s clear that the
double–layers formed twofold interpenetration structure along the
55 c axis (Fig. 7c).
Thermal analysis complexes 1–5’. Thermogravimetric
105 experiments were conducted to study the thermal stability of
complexes 1–5’ (Fig. S12). In the TGA curve of 1, there is one
continuous weight–loss step. The weight loss of 72.15% in the
temperature range of 368~492 °C corresponds to two TMCBA–
anoins which is in accordance with the calculated value of 78.25%.
110 The TGA curve shows that 2 has three weight–loss stages. The first
weight–loss of 3.80% in the temperature range of 62~90 °C is
attributed to the loss of one coordination water molecule. The
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5
10
15
20
25
30
35
Fig. 8 Normalized emission spectra of complexes 1–5’ at 298 K, 77 K, and TMCB, 1,4–H2bda at 298 K in solid state and the corresponding color
coordinate diagram of emission.
40 value is close to the calculated value of 3.76%. The loss of 35.12% °C, is assigned to the loss of four DMF molecules (calcd: 26.06%).
occurring at the second step is attributed to one 1,4–bda2- anion in 60 The second weight loss of 44.21% from 380 °C to 490 °C
the range of 160–252 °C (calcd: 34.28%). The third weight–loss of corresponds to the decomposition three 1,4–bda2- anions.43 1 and 4
40.06% at 252–360 °C is considered as the one TMCB ligand possess high thermal stability，which deserves to be explored for
(calcd: 38.48%). Then the TGA of 3 shows three step weight–loss the application in DSSCs.
45 process, the first weight–loss of 6.34% in the temperature range of
276–295 °C, and the following weight–loss of 23.34% during 300– 65 Luminescence properties: Inorganic−organic hybrid
390 °C, which corresponds to the set free of two coordination coordination complexes, especially with d10 metal centers, have
water molecules, three free water molecules (calcd: 6.53%) and the been investigated for luminescence properties owing to their
two 1,4–bda2- anions (calcd: 23.79%), respectively. The third step potential applications as luminescent materials.44 The emission
50 loses weight from 400 °C to 500 °C corresponding to the loss of spectrum of solid–state sample (Fig. 8) of 1 is centered at 461
four TMCB ligands (obsd: 54.26%, calcd: 53.39%). For 4, the first 70 nm (455 nm for 2, 449 nm for 3, 436 nm for 4, 438 nm for 5,
weight loss from 240 °C to 316 °C is attributed to the release of 433 nm for 5’, 408 nm for TMCB and 405 nm for 1,4–H2bda),
two coordinated water molecules, two free water molecules and exhibiting deep blue, blue and light blue luminescent emissions
two free nitrate ions (obsd: 12.45%; calcd: 12.82%). The second with CIE (Commission Internacionale d’Eclairage) coordinates
55 weight loss of 71.15% (calcd: 70.49%) from 390 °C corresponds to of 1–5’ at 298 K (Fig. 8). These luminescent emissions may be
the loss of four TMCB ligands. 5 and 5’ are supramolecular 75 attributed to the ligand-centered π*→π transition (Scheme 3).45
isomers, therefore, the thermal behaviors of 5 and 5’ display two However, the role of structural complexity and framework
similar weight loss steps. The first of 26.85% from 200 °C to 380
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blue and light blue luminescence emissions with CIE
coordinates, which are affected by the solvent and temperature.
60 The 1H NMR data indicates that 1–5’ still keeps polymeric
structure in solutions and don’t decompose.
5
10
15
Application in DSSCs: Encouraged by the UV absorption in
three solutions results, complexes 1 and 4 can be considered as
co-sensitizers used in N719 sensitized DSSCs. The absorption
65 spectra of the prepared complexes 1, 4 and N719 in ethanol
solutions are shown in Fig. S19, and the corresponding data are
listed in Table 1. The electronic absorption spectra of 1 and 4
exhibit two energy absorption bands: two higher energy
absorption bands at 331 nm and 324 nm, two low energy
70 absorption bands at 378 nm and 365 nm. Compared with the
absorption spectra of N719, apparently, the absorption spectra
of 1 and 4 could compensate for that of N719 in the low
Scheme 3 Schematic energy level diagram of complexes 1–5’ molecular wavelength region of ultraviolet and blue-violet.
orbitals (a, π→π*; b, π*→π; c, MLCT; d, LMCT).
As shown in Table 1, the UV absorption (λmax) appears at
75 378 nm for 1 and 365 nm for 4. The molar extinction
robustness cannot be ignored. Considering the above factors, it coefficients in the blue-violet region are 47,016 M-1 cm-1 for 1
20 is equally difficult to assign its emissions, as it is neither and 45,123 M-1 cm-1 for 4. All of these are much higher than
metal–to–ligand charge transfer (MLCT) nor ligand–to–metal that of the ruthenium complex N719.49 A higher molar
charge transfer (LMCT) (Scheme 3).
extinction coefficient indicates that the 1 and 4 possess a higher
The solid state luminescence spectra of 1–5’ at liquid 80 light harvesting ability in this wavelength region compared
nitrogen temperature are researched. At 77 K, 1–5’ emits with N719 and I3- (25,000M-1 cm-1).50 Hence it can be predicted
-
25 intensely at 509 nm, 501 nm, 496 nm, 472 nm, 481 nm and 478 that the photon lost due to the light absorption by I3 will be
nm, which are at the deep green and green (Fig. 8). The change suppressed by the use of 1 or 4 as a co-sensitizer and co-
-
of temperature from 298 K to 77 K caused a bathochromic shift adsorbent due to the competition between 1 or 4 and I3 to
of emission peaks in solid state of 1–5’. The shift in 85 absorb light.
luminescence spectra at low temperatures so called
On the other hand, energy–level matching is crucial in
30 “luminescence thermochromism” is usually explained by selecting sensitizer. In order to estimate the HOMO and LUMO
predomination “cluster centred”.46 There are more free water energy levels of 1 and 4, cyclic voltammetry (CV) was carried
molecules in 3 than that in 2, which can increase the out in
a three–electrode cell and an electrochemistry
radiationless transition and cause blue shift for the maximum 90 workstation (Fig. S20). The experimental data for
emission. Besides that, we can conclude that the shift of the electrochemical properties of complexes are summarized in
35 maximum emission in 1−5’ may be attributed to the rigidity of Table 1. As estimated from the intersection of the absorption
complexes 1−5’. This rigidity is favor of energy transfer and and emission spectra, the excitation transition energy (E0–0) of
reduces the loss of energy through a radiationless pathway. The 1 and 4 are 3.10 and 3.15 eV, respectively. Consequently, the
possible explanation for the difference emission properties of 95 HOMO values of 1 and 4 are calculated based on their first
1−5’ is the different dimensionality in 1−5’.
redox potentials as –5.32 and –5.41 eV, respectively, and the
40
We also performed time–resolved measurements by using LUMO levels of 1 and 4 calculated from EHOMO + E0–0, are –
the time–correlated single photon counting (TCSPC) technique. 2.22 and –2.26 eV, respectively.51 The HOMO and LUMO
The luminescent lifetimes of 1–5’ increase to those at 298 K energy levels of 1 and 4 are shown in Scheme 4. It shows that
(298 K: τ = 9.53 µs, 11.17 µs, 12.26 µs, 9.66 µs, 9.83 µs, 12.48100 the energy levels of 1 and 4 are appropriate for the DSSCs
µs for 1–5’; 77 K: τ = 18.04 µs, 16.63 µs, 18.22 µs, 11.87 µs, system containing TiO2. The LUMO levels lied above the
45 18.23 µs, 16.16 µs for 1–5’) (Fig. S13), since cold conditions conduction band (CB) of the TiO2 semiconductor (-4.40 eV vs
would be favorable to the rigidity of ligands with reducing the vacuum), indicating efficient electron injection, and the HOMO
-
non–radiation decay and collisional quenching.47
energy levels lied below the I-/I3 redox electrolyte (-4.60 eV vs
For 1-5’, we have further examined the effects of solvent105 vacuum) which is further improved negatively about 0.3 V by
-
polarity on the UV absorption at 298 K, the emission adding additives such as 4-tert-butyl pyridine (TBP) to the I-/I3
50 sensitivity, luminescent lifetimes and the quantum yields (Φ) at redox electrolyte,52 providing sufficient driving force for dye
298 K and 77K (Fig. S14–Fig.S18), corresponding data are regeneration.53
listed in Table S1. In the UV spectra, the electronic absorption
Therefore, complexes 1 and 4 were employed as co–
spectra of 1–5’ are similar to that of free ligands, which is110 sensitizers and co–adsorbents to fabricate complex/N719
attributed to the metal perturbed intraligand π→π* transition photoanodes. The current–voltage (J–V) characteristic of the
55 (Scheme 3).48 Among them, 1 and 4 have strong absorption in DSSCs devices based on N719, 1, 4, 1/N719 and 4/N719
the low wavelength region of ultraviolet and blue-violet. photoanodes are shown in Fig. 9, and the corresponding cells
Complexes 1–5’ in different dilute solutions display deep blue, performance are summarized in Table 2. The values of Jsc is
115
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Table 1 Experimental data for spectral and electrochemical properties of the complexes 1 and 4
Eox/V vs SCEd
0.92
Dyes
λabs(nm)a
378
ε(M–1cm–1)a
47016
λem(nm)a,b
414
E0–0(eV)c
3.10
EHOMO(eV)e
–5.32
ELUMO(eV)e
–2.22
1
4
1.01
365
45123
395
3.15
–5.41
–2.26
a Absorption and emission spectra were recorded in ethanol solution (10–5 M) at room temperature.
b Complexes were excited at their absorption maximum value
c Optical band gap calculated from intersection between the absorption and emission spectra.
d The first oxidation potentials of complexes were obtained by CV measurement.
5
10
15
20
25
e The values of EHOMO and ELUMO were calculated with the following formula:
ox
onset
HOMO (eV) = -e(E V + 4.4V); LUMO (eV) = EHOMO + E0-0
where E0–0 is the intersection of absorption and emission of the complexes 1 and 4.
50
55
Scheme 4 Schematic energy diagram of HOMO and LUMO for dyes
60 Fig. 9 J–V curves for DSSCs based on co–sensitized photoelectrodes and
N719, 1, 4 sensitized photoelectrode under irradiation.
compared to the energy levels calculated for TiO2.
improved in the order of 1/N719 > 4/N719 > N719 > 1 > 4
respectively. The 1/N719 and 4/N719 device yield Jsc of 17.99 mA
30 cm–2 and 16.69 mA cm–2, Voc of 0.70 V and 0.71 V, fill factor (FF)
of 0.61 and 0.58, η of 7.68% and 6.85%. The parameter of η is
40.40% and 25.23% higher than that of the device only sensitized
by N719. However, the individually 1 and 4 sensitized devices
were found to exhibit a low η value of 0.02% and 0.01%, Jsc of
35 0.14 mA cm–2 and 0.12 mA cm–2, Voc of 0.28 V and 0.25 V, FF of
0.40 and 0.37.
65
70
Table 2 J–V performance of DSSCs based on different photoelectrodes
Photoelectrode Jsc/mA/cm2 Voc/V
FF
η/%
1/TiO2
4/TiO2
N719/TiO2
1/N719/TiO2
4/N719/TiO2
0.14
0.12
12.78
17.99
16.69
0.28
0.25
0.69
0.70
0.71
0.40
0.37
0.62
0.61
0.58
0.02
0.01
5.47
7.68
6.85
75
Fig. 10 The incident photon-to-current conversion efficiency spectra of
devices based on single N719, 1,
4 sensitized and co-sensitized
The enhanced Jsc value is ascribed to the enhanced IPCE
80 photoanodes.
40 response of the cell, since they are related by the equation:
the prepared complexes are used as co-sensitizer, this decrease is
restored a lot. This means the co-sensitization of N719 and
prepared complexes has a significant synergy and compensatory
85 effect on light harvesting, electron injection and collection on TiO2.
Based on the IPCE and the absorption spectra, the cell’s higher Jsc
in the case of co-sensitization is mainly ascribed to better light
harvesting in the low wavelength region, where the absorption of
N719 is compensated and the competitive light absorption of
ph.AM1.5G ()d
J  e
sc
where e is the elementary charge and

ph.AM1.5G is the
photon flux at AM 1.5.54 The IPCE spectra of different devices
were collected in Fig. 10. The DSSCs containing only N719
45 dye has a broad IPCE spectrum from 300-750 nm but a
decrease in the wavelength range of 340-450 nm, which is due
-
to the competitive light absorption between I3 and N719. When
8
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Journal of Materials Chemistry A
5
10
15
Fig. 11 Nyquist plots of EIS for DSSCs based on different photoelectrodes measured under standard AM1.5 G solar irradiation (a) and in dark (b) at
forward bias –0.75V.
-
I3 is overcome. On the other hand, the bad IPCE response of 1 as the nitrogen atom in pyridine.57 While, adsorption on Nano
and 4 individually sensitized DSSC is the reason of its low Jsc. 60 TiO2 surface through carboxyl, making its excited electron
20 And the Jsc in co-sensitized devices is not a result of easily injected into the conduction band of Nano TiO2. This is
summation. However, this confirms that there is a significant the reason why complex 1 obtained a higher efficiency than
synergy and compensatory effect between 1 or 4 and N719.
complex 4 when they were co-sensitized with N719,
We utilized electrochemical impedance spectroscopy (EIS) respectively.
to analyze charge carrier dynamics in the interfacial regions of
25 solid–liquid layers. Usually, in DSSCs system, each EIS curve
65 Conclusion
contains three semicircles that are representative for the
In conclusion, six new complexes have been successfully
synthesized through the hydro(solvo)thermal reactions of
Cd(II) salts with the new multifunctional ligand TMCB.
Through controlling the reaction conditions, TMCBA was
70 obtained from the cyanophoric hydrolytic reaction. Complexes
1–5’ exhibited mononuclear, 1D, 2D and 3D architectures,
respectively. The structural diversities of the complexes
indicate that the TMCB ligand is good candidates for the
construction of complexes with fascinating motifs. The tunable
75 luminescence emissions show that the complexes 1–5’ may be
good candidates for photoactive materials. It is anticipated that
other new complexes with intriguing structures as well as
chemical or physical properties may also be synthesized
through using the 4-(1,2,4-triazolylmethyl) cyanobenzene
80 ligand. It’s worth noting that, complexes 1 and 4 can be applied
with N719 in DSSCs as a co-sensitizer, which will enhance the
photo-electricity efficiency and improve both Jsc and Voc. The
co-sensitized devices exhibit an enhanced performance, and
both of them are higher than that of single N719 sensitized
85 solar cells. Complexes 1 and 4 co-sensitized device yields the
overall efficiency of 7.68% and 6.85%, which is 40.40% and
25.23% greater than that of the device containing only N719
(5.47%). The newly developed co-sensitizer is anticipated to
arouse broad interest in further boosting the efficiency of dye
90 sensitized solar cell by a simple sequential adsorption process,
which explores a new domain for the use of these type
complexes.
resistance states of different interfaces.55 The three semicircles
located in high, middle and low frequency regions (left to
right) are attributed to the electrochemical reaction at the
30 Pt/electrolyte interface, the charge transfer at the
TiO2/dye/electrolyte interface and a Warburg diffusion process
of the I-/I3- in the electrolyte.56
Under light illumination, EIS was utilized to analyze the
charge transport resistance at the TiO2/dye/electrolyte interface
35 for its significance on the efficiency of DSSCs. As shown in
Fig. 11a, The radius of the large semicircle located in middle
frequency regions in the Nyquist plots decrease after co–
sensitized with complexes, and the values are in sequence for
1/N719 < 4/N719 < N719, which indicates a decrease of the
40 electron transfer impedance and an increase of charge transfer
rate at this interface after co–sensitization. while in the dark,
this semicircle radius in the Nyquist plot increased after co-
sensitized with complexes, and the values are in the order of
1/N719 > 4/N719 > N719, which indicates an increase of
45 electron recombination impedance and a reduction of the
interfacial charge recombination rate (Fig. 11b). Higher charge
transfer rate and lower charge recombination rate are benefit
for enhancing performance of DSSCs.
For complex 1, it adsorbed on Nano TiO2 thin film surface
50 through carboxyl which has various coordination modes with
metal ions, such as bidentate-monatomic, chelate-monatomic,
etc. Although carboxyl has coordinated to the Cd2+ ion in
complex 1, Ti4+ ion may also be coordinated with carboxyl due
to the existence of lone pair electrons in carboxylate oxygen
55 atom which could combine with Ti4+ ion to form Ti-O
coordination bond, and further adsorbed on the TiO2 film.
While for complex 4, the nitrogen atoms of 1,2,4-triazole were
expected to adsorb at the Lewis acid sites of the TiO2 surface
Acknowledgements
This work was supported by National Natural Science
95 Foundation of China (Grant 21371040 and 21171044), the
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Journal of Materials Chemistry A
DOI: 10.1039/C4TPA0a6g67e1E10 of 11
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Journal of Materials Chemistry A
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DOI: 10.1039/C4TA06671E
Table of Content
Application in dye–sensitized solar cells and luminescence properties:
an insight into the controllable synthesis of Cd(II) complexes with the
new multifunctional ligand
Song Gao,a Rui Qing Fan,*,a Xin Ming Wang,a Liang Sheng Qiang,a Li Guo Wei,a Ping Wang,a
Hui Jie Zhang,a Yu Lin Yang*,a, Yu Lei Wangb
aDepartment of Chemistry, Harbin Institute of Technology, Harbin 150001, P. R. of China
bNational Key Laboratory of Science and Technology on Tunable Laser, Harbin Institute of Technology,
Harbin 150080, P. R. of China
This synergism, resulting from the combination of luminescence and DSSCs, opens up the
way to new multifunctional materials.