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Reactivity of the (trans-Pt(PMe3)2(C≡CC6H4SMe)2) Ligand with Copper Cyanide: Formation of the [Cu22-C≡CC6H4SMe)2]n Polymer

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Abstract

The organometallic ligand trans-Pt(PMe3)2(C≡CC6H4SMe)2, L1, reacts with C≡N ions (as sodium salt) in various stoichiometric ratios to form L3, [trans-Pt(PMe3)2(C≡N)2], and MeSC6H4C≡C anions, which were identified using various spectroscopic techniques (1H and 31P NMR, and ESI-TOF). Concurrently, the capture of the released MeSC6H4C≡C units by Cu(I) metals was observed when L1 was reacted with CuCN in excess. In this case, two new coordination polymers (CPs), [Cu(μ2-C≡CC6H4SMe)]n (CP1) and [CuCN(L2)]n (CP2) where L2 is the new ligand [trans-Pt(PMe3)2(C≡CC6H4SMe)(C≡N)] formed along with the [trans-Pt(PMe3)2(C≡N)2] complex in small amount. CP1 was also synthesized independently to secure its identification. CP1 was found to be emissive at both 298 and 77 K. The nature of its emissive excited state was found to be an intraligand MeSC6H4C≡C3ππ* mixed with some atomic contributions of the copper(I) d-orbitals based on DFT computations.

Graphic Abstract

Introduction

The term organometallic ligand was first used in the 1960’s [1]. The main purpose of the new ligand design was to assemble two moieties, metallic centers and organic moieties, which together exhibit distinctive physical (optical, redox) and chemical (catalytical) properties, for targeted combined functions [2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19]. Although the field is dominated by ferrocenyl- and η5-cyclopentadienyl-containing organometallic ligands, a few other types of motifs were also reported [4, 10], including interesting examples using platinum(II) as the metallic center [3, 9, 14, 16]. The ethynyl center of the so-called “robust” trans-Pt(PR3)2(C≡CC6H5)2 (R=Ph) complex was reported to bind Cu(I) [20] and Ag(I) [21] metals via (η2-C≡C)-M linkages to form mixed-metal 1D-organometallic polymers (CPs). However, literature shows that the field is still rather explorative [2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21].

This trans-Pt(II) motif can be functionalized further at the para-positions of the benzene rings to design new polydentate organometallic ligands. Indeed, new coordination and organometallic polymers with Cu(I) [3, 22, 23] and Au(I) [24] metals have recently been prepared (see L1 as an example; Fig. 1). In this preliminary communication, a new type of reactivity for ligand L1 towards a Cu(I) salt is reported. Indeed, it is demonstrated that cyanide ions, in various stoichiometric amounts, displace the MeSC6H4C≡C fragments in L1 to unexpectedly form a new organometallic ligand, L2 (Fig. 1), which is found anchored as a pendent group in a new CP, [CuCN(L2)]n (CP2). The MeSC6H4C≡C units released during the reaction with CuCN are captured by Cu(I) ions to form an emissive organometallic polymer [Cu(μ2-C≡CC6H4SMe)]n (CP1). Moreover, L2 and a small amount of the known complex [trans-Pt(PMe3)2(C≡N)2], L3 are also obtained when L1 reacts with NaCN [25]. The emission properties of CP1 were investigated and interpreted with the aid of DFT computations. Altogether, L1 was believed to be robust up to now, but this work shows a limitation to the application of this organometallic ligand when in the presence of an excess of a strong ligand such as cyanide.

Fig. 1
figure1

Structures of L1L3

Experimental Section

Materials

The [trans-Pt(PMe3)2(MeSC6H4C≡C)2] (L1), 4-ethynylthioanisole [22, 23] and [trans-Pt(PMe3)2(C≡N)2] (L3) complexes [25] Cu2(OH)3OAc·H2O [26] and [Cu(μ2-C≡CC6H4SMe)]n polymer [27] were prepared according to literature procedure. CuCN was purchased from Sigma-Aldrich and was used as received.

Synthesis of the [Cu(μ2-C≡CC6H4SMe)]n Polymer (CP1)

Cu2(OH)3OAc·H2O (0.302 g, 1.18 mmol) and 4-ethynylthioanisole (0.588 g, 3.96 mmol) were suspended in 60 mL of methanol in a 100 mL round bottom flask. The reaction mixture was stirred at 32 °C for 2 days. The mixture was filtered and washed with dichloromethane. The yellow paste was fully dried under vacuum. Yield: 94%. Anal. Calcd for MeSC6H4C≡CCu: C, 51.29; H, 3.35%. Found: C, 51.07; H, 3.54%. Raman: 1925 cm−1C≡C); 1592 cm−1C=C).

Reactivity ofL1with NaCN. L1with NaCN. 1:1 Ratio, (L1:NaCN)

L1 (20.0 mg, 0.03 mmol) is placed in a vial containing 4 mL of degassed acetonitrile by bubbling with argon for 15 min. A solution of NaCN (3.1 mg, 0.03 mmol) dissolved in 2 mL of methanol (used as received) was added. The mixture was stirred for 1 h and slightly heated at 60 °C for 10 min. The resulting solution was slowly cooled down to room temperature. After 3 days upon standing, some bright yellow crystals formed and were separated from the solution by transferring it into another vial. The crystals were dried in air and analyzed. These crystals turned out to be unreacted L1 based on 1H NMR and 31P NMR spectra compared with an authentic sample (1H NMR (300 MHz, CDCl3) δ 7.23 (d, J = 2.0 Hz, 4H), 7.11 (d, J = 8.4 Hz, 4H), 2.45 (s, 6H), 1.84—1.66 (m, 18H). 31P NMR (122 MHz, CDCl3): δ − 20.51 (s, JPt−P = 2300 Hz)). The solution was left to evaporate at room temperature. Two products were identified: L1 (1H NMR (300 MHz, CDCl3) δ 7.22 (d, 4H), 7.11 (d, J = 8.4 Hz, 4H), 2.45 (s, 6H), 1.88—1.70 (m, 36H). 31P NMR (122 MHz, CDCl3): δ − 20.51 (s, JPt−P = 2300 Hz)), and L3 (31P NMR (122 MHz, CDCl3): δ − 20.06 (s, JPt−P = 2112 Hz)), [trans-Pt(PMe3)2(C≡N)2], m/z Calc.: 422.0486 [M + Na]+. m/z Found.: 422.0490 [M + Na]+), both based on the comparison with authentic samples. The released MeSC6H4C≡C or MeSC6H4C≡CH was not observed in this case, presumably due to its low concentration.

L1 with NaCN. 1:2 Ratio (L1:NaCN)

The reaction was performed in a similar manner as stated above: L1 (20.0 mg, 0.03 mmol) and NaCN (6.2 mg, 0.06 mmol) were used. After 3 days, some bright yellow crystals formed, which were confirmed to be L1, and a small amount of white precipitate also appeared, which was identified to be L3. The remaining solution was transferred in another vial was left to evaporate at room temperature and two products were identified: 31P NMR (122 MHz, CDCl3): δ − 20.51 (s, JPt−P = 2300 Hz) (L1), and δ − 20.06 (s, JPt−P = 2112 Hz) (L3), again both based on authentic samples for comparison. The released MeSC6H4C≡C or MeSC6H4C≡CH was also observed in this case based on 1H NMR provided in SI.

L1 with NaCN in 1:3 Ratio (L1:NaCN)

The reaction was performed in a similar manner as stated above: L1 (20.0 mg, 0.03 mmol) and NaCN (9.3 mg, 0.09 mmol) were used. After 3 days, only a white precipitate appeared, which was identified as L3. The remaining solution was transferred in another vial and was left to evaporate at room temperature. Two products were identified as MeSC6H4C≡CH: 1H NMR (300 MHz, CDCl3): δ 7.40 (d, J = 8.5 Hz, 2H), 7.17 (d, J = 8.5 Hz, 2H), 3.06 (s, 1H), 2.48 (s, 3H). The white precipitate is also analyzed separately and turns out to be L3. 1H NMR (300 MHz, CDCl3) δ 1.92–1.73 (m, 18H). 31P NMR (122 MHz, CDCl3): δ − 20.07 (s, JPt−P = 2112 Hz). There was no evidence for the presence of unreacted L1.

Reactivity of L1 with CuCN

L1 (30.0 mg, 0.046 mmol) and CuCN (12.6 mg, 0.14 mmol) were added in a vial containing a 5 mL of acetonitrile which was degassed by bubbling the solvent with argon for 15 min. The mixture was stirred for 4 h at room temperature and heated at 70 °C for 3 h. The obtained solution is cooled slowly to room temperature leading to the formation of light-yellow crystals as well as yellow powder. The mixture of crystals and powder were dried in air (yield = 64%). The crystals were manually separated from powder under a microscope, which turns out to be CP2 based on X-ray crystallography (see below). The powder was identified to be CP1 (see text).The remaining solution was transferred into another vial and was left to evaporate at room temperature yielding a small amount of light pale-yellow product identified as L2: anal. calcd for C16H25NP2PtS (520.46): C, 36.92; H, 4.84; N, 2.69%. Found: C, 37.22; H, 4.79; N, 2.63%. IR: 2978, 2914 cm−1C–H); 2130 cm−1C≡N); 2115 cm−1C≡C); 1484 cm−1C=C). Raman: 2980, 2909 cm−1C–H); 2130 cm−1C≡N); 2115 cm−1C≡C); 1588 cm−1C=C). m/z Calc.: 543.0725 [M + Na]+. m/z Found.: 543.0731 [M + Na]+. 1H NMR (300 MHz, CDCl3) δ 7.22 (d, J = 8.3 Hz, 2H), 7.12 (d, J = 8.5 Hz, 2H), 2.46 (s, 3H), 1.83–1.70 (m, 18H). 31P NMR (122 MHz, CDCl3): δ − 20.36 ppm (s, JPt−P = 2213 Hz).

Instruments

Solid state UV–Vis spectra were recorded on a Varian Cary 50 spectrophotometer at both 298 K and 77 K using raised-angle transmittance apparatus and a homemade 77 K sample-holder. Steady state emission and excitation spectra were measured on a Edinburgh Instruments FLS980 phosphorimeter equipped with single monochromators. The steady state emission spectra were recorded using capillaries for the solid state, an NMR tube for the 77 K measurements, and an air tight 1 cm cuvette for measurements in solution at 298 K, which were prepared in a glove box. These spectra were corrected for instrument response. The phosphorescence lifetime measurements were performed with an Edinburgh Instruments FLS980 phosphorimeter equipped with “flash” pulsed lamp. The frequency of the pulse was be adjusted from 1 to 100 Hz. All lifetime values were obtained from deconvolution and distribution lifetime analysis and multi-exponential analysis for comparison purposes. Solid state emission quantum yield was recorded using a Quanta-φ F-3029 integration sphere plugged into a Horiba Fluorolog III. This instrument was equipped with an integration sphere which allowed for the direct measurements of emission quantum yields. The IR spectrum was measured using ABB Bomem, MB series FT-IR instrument. 1H and 13P NMR were recorded on Bruker Avance 300 Ultrashield NMR spectrometer using CDCl3 and CD2Cl2 as solvents. The solid-state Raman measurement was recorded on a Bruker RFS 100/S spectrometer.

Powder XRD

Powder X-ray diffraction for CP1 was measured on a Bruker APEX DUO X-ray diffractometer with a total number of six correlated runs per sample was done with Phi Scan of 360o. The sample was then exposed to 270 s on the Cu micro-focus anode (1.54184 Å) and the CCD APEX II detector at 150 mm distance. The runs were collected from − 12 to − 72°2θ and 6 to 36° ω were treated and integrated with the XRW2 Eval Bruker software to produce WAXD diffraction patterns from 2.5 to 80°2θ. The patterns were treated with Diffrac.Eva version 2.0 from Bruker.

Computation (for CP1)

The density functional theory (DFT) calculations were performed with Gaussian 16 [28] at the Université de Sherbrooke with the Mammouth supercomputer supported by Le Réseau Québécois De Calculs Hautes Performances. The cif file from X-ray crystal structure for [Cu(μ2-C≡CC6H5)]n have been used for the calculation. The DFT (ground and triplet states) calculations [29,30,31,32,33,34,35,36,37,38] were carried out using the B3LYP (unrestricted B3LYP for the triplet) method. The 6–31 g* basis set was used for C, H atoms. [38] VDZ (valence double ζ) with SBKJC effective core potentials were used for all Cu atoms [39,40,41,42,43,44].

X-Ray Structure Determination (CP2)

A clear light-yellow prism-like specimen of CP2 was measured on APEX DUO system equipped with a TRIUMPH curved-crystal monochromator and a Mo Kα fine-focus tube (λ = 0.71073 Å). A total of 797 frames were collected. The frames were integrated with the Bruker SAINT [45] software package using a wide-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total 11,415 reflections to a maximum θ angle of 26.44° (0.80 Å resolution), of which 4492 were independent (average redundancy 2.541, completeness = 99.5%, Rint = 9.33%, Rsig = 11.28%) and 2791 (62.13%) were greater than 2σ(F2). Data were corrected for absorption effects using the multi-scan method (SADABS). [45] The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group C 1 2/c 1, with Z = 8.

Results and Discussion

When L1 is reacted with NaCN in various stoichiometric ratios, the known coordination complex L3 and MeSC6H4C≡C (as Na+ salt, which becomes MeSC6H4C≡CH in the presence of humidity) are observed by 1H and 31P NMR, and ESI-TOF, depending upon the initial L1/NaCN ratios (1:1, 1:2, and 1:3; Scheme 1). The resulting solution contains unreacted L1 for the ratios 1:1 and 1:2, but the conversion is completed for a ratio of 1:3. Conclusively, despite the believed notion that the trans-Pt(PR3)2(C≡CC6H4X)2 motif is robust (X = functional group; R = aryl, alkyl) [46], the MeSC6H4C≡C moieties can be displaced with an excess of CN‾ ions. Consequently, different CPs are then anticipated to be formed when the counter cation is the Cu(I) metal in comparison with that is reported for CuX salts (X = I, Br, Cl) [22, 23].

Scheme 1
scheme1

Reactivity of L1 with NaCN: i) MeCN/MeOH, in 1:1, 1:2, 1:3 L1/NaCN ratios

This is indeed the case (Scheme 2). Two CPs were identified in the reaction mixture along with a small amount of L2, which remains soluble in the solvent. This latter ligand was characterized by mass spectrometry, IR and Raman spectroscopy, and chemical analysis (the details are placed in the SI). Single crystals for the first product were exhaustively separated from the powder mixture under a microscope and analyzed. The X-ray structure data reveals that a CP of general formula [CuCN([trans-Pt(PMe3)2(C≡CC6H4SMe)(C≡N)])]n (CP2) is formed (Figs. 2 and S20, Tables S1 and S2). This CP consists of a typical 1D zig-zag (CuCN)n chain bearing pendent groups, L2 (Fig. 1) [47,48,49,50,51,52,53,54,55,56,57,58,59,60].

Scheme 2
scheme2

Reactivity of L1 with CuCN: i) MeCN at 70 °C, 1:3 L1/CuCN ratio

Fig. 2
figure2

Representation for a fragment of the 1D zigzag chain in CP2. Colour code: yellow = S, silver = Pt, sky blue = N, brown = Cu, orange = P, black = C. H atoms are removed for clarity (Color figure online)

The interesting feature is that L2 was never observed when L1 was reacted with NaCN, thus suggesting that the Cu(I) ion scavenges L2 as soon it is formed. However, its capture is not total since some small amounts of L3 is still detected (by 31P NMR) in the remaining solution. In addition, despite the fact that CuCN is capable of promoting C≡C–C≡C coupling [61], this Glaser-type compound was not detected. Concurrently for the other product (subsequently denoted as CP1), multiple attempts to recrystallize the remaining reaction powder mixture stubbornly failed. However, this second CP was easily identified into two steps by first comparing its powder XRD with that for the related organometallic polymer [Cu(μ2-C≡CC6H5)]n [27]. In this case, the resemblance is striking and allows one to suggest that the general formula is [Cu(μ2-C≡CC6H4SMe)]n for CP1 (Fig. 3). The second step consists in preparing an authentic sample using the same protocol outlined for the synthesis of the known CP [Cu(μ2-C≡CC6H5)]n [27], and then again compare their powder X-ray patterns. This experiment was performed and confirmed unambiguously the identity of CP1.

Fig. 3
figure3

Left: comparison of the powder XRD patterns of [Cu(μ2-C≡CC6H5)]n (calculated, black) and CP1 (experimental, red). Right: structure of [Cu(μ2-C≡CC6H5)]n showing the unit cell box and the (1,0,0) plane (Color figure online)

In addition, the strongest signal in the vicinity of 2θ ~ 6° is due to the (1, 0, 0) plane corresponding to the a axis of the crystal lattice [27]. The calculated distances interplanar are 14.64 and 15.59 Å for [Cu(μ2-C≡CC6H5)]n and CP1, respectively. This increase is fully consistent with the presence of the larger SMe groups instead of H in CP1. By indexing the measured PXRD of CP1, the a axis in the lattice is found to be 16.12 Å (a = 16.12, b = 5.38 and c = 9.57 Å with the calc. V: 800.59 Å3. The identification of CP1 also permits to confirm that the released MeSC6H4C≡C fragments are captured by the “naked” Cu(I) ions. Because the CuCN salt is used in a given and necessary excess (1:3 instead of 1:2 L1/CuCN), the remainder CN ions react with L1 to form L3 (Scheme 1), which is found inside the solution. Indeed at the end, no residual CuCN is left as confirmed by the absence of its characteristic sharp emission at ~ 400 ± 10 nm at 298 and 77 K as verified with an authentic sample (Supporting Information).

A new organometallic polymer, CP1, is generated and is issued from a totally unexpected process (L1 + CuCN). Interestingly, CP1 is emissive (Fig. 4), which is consistent with the fact that [Cu(μ2-C≡CC6H5)]n is also found luminescent. Its emission signature is, without a surprise, reminiscent to that of [Cu(μ2-C≡CC6H5)]n [27], and the related linear cluster [(TripC≡CC≡CCu)20(MeCN)4] (Trip = 4,6-triisopropylphenyl) (Table 1) [62].

Fig. 4
figure4

Absorption (black), excitation (blue), and emission (red) spectra of CP1 at 298 (left) and 77 K (right). The chromaticity diagrams are placed in the Supporting Information (Color figure online)

Table 1 τe data for CP1 at 298 and 77 K (decays are placed in SI)

The presence of vibronic structure in the emission band strongly suggests the presence of a ππ* excited state mainly localized on the C≡CC6H4SMe unit. The emission bands at 298 and 77 K decay in the μs timescale, which is consistent with of what is reported in the literature for Cu–CCAr species [63,64,65,66], but in these cases the decay traces are poly-exponential with sub-μs components. Bi-exponential traces and sub-μs components have occasionally been observed in the past in Cu–Cu-bonded [67] and Cu–Ag-bonded [68] clusters containing Cu–C≡CAr bonds (Ar = aromatic group). The shorter τe values and the bi-exponential behaviour was explained by variable temperature 1H and 31P NMR where evidence for fluxionality of the Cu22-C≡C(η2)Ar arms was shown [67].

Literature shows only a handful of investigations devoting computational efforts to describe the nature of the emissive excited states of small Cu–Cu-bonded clusters containing Cu–C≡CAr pendent groups [66, 69,70,71,72], but to the best of our knowledge, none on their corresponding polymers were studied. Noteworthy, the size of the microcrystals used to extract the photophysical properties may perhaps be very small, but nonetheless, there are still far more internal Cu atoms than terminal ones. For example, for a [Cu(μ2-C≡CC6H5)]n particle of ~ 0.01 mm radius (i.e. ~ 105 Å), the 1D-chain is built by ~ 104 unit cells implying the use of ~ 4 × 104 internal copper atoms, with respect to 4 terminal ones. Consequently, the design of an appropriate 1D-model is limited by its size. Moreover, the identity of the terminal groups in 1D polymers are rarely known. In this work, the strongest ligand available in solution during the reaction is MeSC6H4C≡C. The model used for the computations is [Cu82-C≡CC6H5)6(C≡CC6H5)6], built upon the cif file of the [Cu(μ2-C≡CC6H5)]n polymer [27]. The SMe groups were not included to save computation time knowing that this does not impact the conclusion. For comparison purposes, the closest computational study on [Cu–C≡CAr]-containing clusters was reported by Yam et al. [69]. Their conclusion was that the emissive triplet excited state is a ππ* state “perturbed” by the presence of some contributions of copper d-orbitals to the MOs. Geometry optimisation on this model in the triplet state was performed and the representations of the frontier MOs are placed in Fig. 5.

Fig. 5
figure5

Top view representations of the frontier MOs for [Cu82-C≡CC6H5)6(C≡CC6H5)6] in its triplet state. The LS-n are the MOs below the LSOMO, and the HS + n are the empty MOs above the HSOMO. Side views are available in the Supporting Information. (HS HSOMO, LS LSOMO)

The lowest energy triplet excited state, T1 (LSOMO/HSOMO), is composed of ππ*-C≡CC6H5 mainly as depicted from the computed atomic contributions (Table 2). Minor contributions from the metals are also computed meaning that T1 is also essentially a ππ*-C≡CC6H5 state “perturbed” by the coordinated copper atoms. This conclusion is fully coherent with that deduced for [Cu–C≡CAr]-containing clusters by Yam and collaborators [69]. Again, the fact that a vibronic progression is observed in the emission spectra of CP1 is a reminiscent general signature and diagnostic for ππ* states. The examination of upper energy Tn states (n > 1; i.e. excited states generated with MOs separated by larger energy gaps between the MOs) based on the data of Table 2, indicates that this conclusion remains for the lowest energy combinations, but as upper energy states are considered, the ratio of the atomic contributions C≡CC6H5 versus Cu decreases and tends to converge towards 50:50.

Table 2 Relative atomic contributions (%) of the various fragments of the frontier MOs for the [Cu82-C≡CC6H5)6(C≡CC6H5)6] model in its triplet state

Final Remarks

An unexpected reactivity of a seemingly robust organometallic ligand (L1) using the strong nucleophile C≡N (as Na+ salt) forming L3 and MeSC6H4C≡C, was observed. In the presence of Cu(I) (as CuCN salt), CP1 and CP2 are formed along with a little amount of uncoordinated L2 with no evidence for C≡C–C≡C coupling bi-product. Its relative fragility may also explain the general paucity of new materials built upon organometallic ligands as stated in the Introduction. For this work, the key features are as follow. First, the MeSC6H4C≡C unit is scavenged by the Cu(I) metal to form an emissive organometallic polymer [Cu(μ2-C≡CC6H4SMe)]n deduced from the comparison of the powder XRD patterns with the structurally related [Cu(μ2-C≡CC6H5)]n polymer. Second, a new ligand organometallic ligand (L2) has been formed and was captured by the CuCN polymeric chain to produce a coordination polymer [CuCN(L2)]n, most likely preventing L2 to become L3 (as observed for the reaction NaCN with L1). The central CuCN chain exhibits the commonly encountered zig-zag geometry. [47,48,49,50,51,52,53,54,55,56,57,58,59,60] The discovery of this new organometallic ligand L2 is interesting since it provides the possibility of using three different coordination sites (–C≡N; –SMe; η2–C≡C) to form new coordination polymers, most likely with variable optical and photophysical properties. Its independent synthesis and characterization, along with those for its coordination polymers with CuX salts will be published in due course. The Supporting Information provides the X-ray crystal data of CP2 as preliminary data. CP1 also exhibits an interesting feature as the -SMe sites do not bind any copper(I) atoms in solution despite its availability. This property also appears to have facilitated its identification (by comparing its powder XRD signature with that for [Cu(μ2-C≡CC6H5)]n). Finally, the nature of the emissive state was addressed by DFT computations, and without a surprise (by comparison with data reported on related clusters), the triplet excited state is a C≡CC6H4SMe-localized ππ* states “perturbed” by the presence of some atomic contributions arising from the copper metals. Moreover, the “fragility” of L1 under harsh conditions and its recently demonstrated relative structural flexibility (the complex can bend during the formation of some 2D CPs) [3] indicate a limited application of the organometallic ligands for the construction of CP-based new materials, including metal-organometallic frameworks where the metal is located within the skeleton of the ligand. A full understanding of their chemistry requires further investigations.

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This work was supported by the Natural Sciences and Engineering Research Council of Canada.

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Juvenal, F., Harvey, P.D. Reactivity of the (trans-Pt(PMe3)2(C≡CC6H4SMe)2) Ligand with Copper Cyanide: Formation of the [Cu22-C≡CC6H4SMe)2]n Polymer. J Inorg Organomet Polym 30, 159–168 (2020). https://doi.org/10.1007/s10904-019-01298-7

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Keywords

  • Organometallic polymers
  • Organometallic ligand
  • Luminescence
  • Copper cyanide
  • DFT compuations