Intriguing Near-Infrared Solid-State Luminescence of Binuclear Silver(I

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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

Intriguing Near-Infrared Solid-State Luminescence of Binuclear Silver(I) Complexes Based on Pyridylphospholane Scaffolds Aliia V. Shamsieva,*,† Elvira I. Musina,† Tatiana P. Gerasimova,† Robert R. Fayzullin,† Ilya E. Kolesnikov,‡ Aida I. Samigullina,† Sergey A. Katsyuba,† Andrey A. Karasik,† and Oleg G. Sinyashin† †

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Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov Street 8, 420088 Kazan, Russian Federation ‡ Center for Optical and Laser Materials Research, Research Park of St. Petersburg State University, Ulianovskaya Street 5, 198504 St. Petersburg, Russian Federation S Supporting Information *

ABSTRACT: A series of novel charged disilver(I) complexes with pyridylcontaining phospholanes was synthesized. These complexes were characterized using a range of spectroscopic techniques and single-crystal and powder X-ray diffraction. The complexes demonstrate solid-state near-infrared (NIR) luminescence (765−902 nm) that is unique for dinuclear AgI complexes. Combined spectroscopic/quantum chemical analysis suggests that the NIR luminescence of complexes 4−6 in the solid state is mainly due to crystal packing effects.

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INTRODUCTION During the past decade, there have been enormous research investigations on the luminescent complexes of transition metals as potential applicants for organic light emitting diodes (OLEDs),1−7 for sensors,8 for contrasting agents,9 or for biomedical purposes.10 Among these studies, near-infrared (NIR) luminescence, particularly in the 700−900 nm region, has been drawing great research interest due to promising applications in night-vision-readable displays11 and sensors,12 as well as in biomedicine due to the maximum penetration of light through biological tissues. 7,13−15 In this regard, lanthanide-based luminophores are one of the current wellknown candidates for NIR applications.11,15−17 This class of compounds provides a useful set of optical properties as NIR luminophores, for example, very sharp emission bands, long luminescence lifetimes, or great robustness toward photobleaching. At the same time, the luminescence of lanthanide complexes is highly susceptible to quenching by high-energy and highly anharmonic molecular oscillators such as C−H stretching vibrations in organic ligands.18,19 To avoid this disadvantage, novel NIR-emitters based on Ir(III) and Ru(II) complexes with perylene bisimides,20 Cr(III) doped gallates/ aluminates/gallogermanates,21,22 and several transition-metal complexes (Re(I), Re(III), Os(II), Pt(II), Pd(II), etc.)23 have been developed. Other promising candidates for NIR-emitters are luminescent complexes of the 11th group metals (Cu, Ag, Au). This © XXXX American Chemical Society

class of compounds garnered significant attention in the past decade due to their low cost, low toxicity, and intense and long-lived luminescence in the solid state at ambient temperatures with emission range spanning the visible spectrum.24−31 The rich photoluminescence of copper group complexes is caused by involvement of metal-to-ligand chargetransfer (MLCT), ligand-to-ligand charge-transfer (LLCT), and metal-halide-to-ligand charge-transfer (M + X)LCT transitions in the emissive state; thus, the emission color of these complexes can be easily tuned by systematic variation of a ligand system.24 From this point of view, P,N-hybrid ligands, particularly phosphinopyridines and their N-heterocyclic analogues, seem to be an invaluable tool for the effective complexation with a transition metal where the N-heterocyclic group implies effective charge transfer between a metal center and ligand(s) and provides luminescence from the obtained complexes. Copper group metal complexes based on P,Nhybrid ligands exhibit a high structural diversity and as a result rich photoluminescent properties.24,27,32−37 The NIR-emissive d10 transition-metal complexes are represented mainly by polynuclear Cu(I) clusters bearing S,N-hybrid ligands23,38−40 and by homo- and heteropolynuclear clusters based on S,N23or P,N-hybrid ligands.41−43 Received: December 13, 2018

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DOI: 10.1021/acs.inorgchem.8b03474 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

are activated in the process. In the case of 4−6, ν1 and ν4 modes are overlapped by ligand vibrations. However, the ν3 bands in all the spectra are broadened, and apart from the main peaks listed above, exhibit shoulders at ca. 1017 and 1113 cm−1 (4), 1017 and 1083 cm−1 (5), 1016 and 1071 cm−1 (6). On the basis of the IR spectra of Cu(BF4)(PPh3)3,59 where the BF4− anion is coordinated to the metal center, the bands at ca. 1016 and 1017 cm−1 can be assigned to the low-energy (A1) component of the ν3(A1 + E) mode of coordinated 10BF4. The bands at 1071, 1083, and 1113 cm−1 can be assigned to the high-energy (E) components of the ν3(A1 + E) mode of coordinated BF4. It should be mentioned that, in the IR spectrum of the initial salt AgBF4, where the anion is coordinated to the Ag+ ion, the ν3 band of BF4− is also broadened and contains several components (1031, 1055, and 1120 cm−1). Additional confirmation of coordination of BF4− to Ag+ is provided by the presence of bands at 352 (for 5) and 353 (for 4 and 6) cm−1 (ν2) in far-IR spectra of the complexes (Figures S10−S12), which should be infrared-inactive in the case of the noncoordinated BF4− anion. The X-ray structures of compounds 4−6 (Figure 1) are similar and represent charged binuclear complexes. In the cationic part, two P,N-bridged ligand molecules of the ligand coordinate two silver ions in a “head-to-tail” mode, which is a common arrangement of P,N-ligands, particularly in binuclear AgI complexes.32,47−49,53 The complex cations are located on the crystallographic inversion centers (Z′ = 0.5). Both silver atoms Ag1 and Ag1i adopt planar T-shaped trigonal geometry considering the metallophilic interaction. The metal core and ligand heteroatoms lie nearly on the same plane and form a five-membered bicycle with the syn-periplanar torsion angle Ag1−N1−C1−P1 of 1.0(4)° (4), −8.8(4)° (5), and −14.6(6)° (6). The Ag···Ag distance (2.7854(8) Å (4), 2.8817(7) Å (5), and 2.7901(10) Å (6)) is significantly shorter than in the charged complexes with (Bzim)Ph2P (1-benzyl-2imidazolyldiphenylphosphine) (2.910(2) Å)54 or dpim (1methyl-2-imidazolyldiphenylphosphine) (2.9932(9) Å).53 The bonds Ag−P (2.3522(11) (4), 2.3725(10) (5), and 2.3564(17) (6)) and Ag−N (2.171(3) (4), 2.192(3) (5), and 2.171(5) (6)) in the investigated complexes are slightly shorter in comparison with the analogues based on (Bzim)Ph2P (2.361(2) and 2.148 Å, respectively)54 or dpim (2.3807(14) and 2.198(4)−2.506(6) Å, respectively),53 which is probably caused by electron donation of the alkyl substituents on the phosphorus atom. The phospholane fragments of the ligands adopt a twisted conformation. Analysis of the environment of the complex cation allows one to observe two types of localization of the tetrafluoroborate anions: (i) where the anions directly contact the silver(I) ions mainly via the short contacts Ag···F and (ii) where the anions are arranged on the periphery of the complexes and are bound to the ligands mainly by means of the hydrogen bonds of a C−H···F type. Unfortunately, the detailed description of the packing of ions in the crystals of 4 and 5 is limited because tetrafluoroborate anions appear to be positionally disordered. Nevertheless, it was found that, taking into account the Ag···F interactions, formation of the infinite chains along the shortest crystallographic direction 0a can be distinguished in the case of complex 4: pairs of tetrafluoroborate anions are situated between two dinuclear cations, and each anion interacts with two silver ions of different complexes in a bridging mode (Figure S13). Interestingly, the crystal structure of 5 is

As compared to the copper(I) compounds, the luminescence of silver(I) compounds is relatively less commonly reported in the literature.25,29,30,44−52 Although photoactive silver(I) compounds have been known for a long time (photography; Ag/Zn and Ag/Cd batteries; antimicrobial and antifungal agents), studying luminescent properties of silver(I) complexes is restricted by the thermal instability and light sensitivity of these compounds that lead to their photodecomposition under ambient conditions. However, there are a lot of stable AgI complexes based on different organic ligands, among which the P,N-hybrid ligands are of special interest. Typically, P,N-ligands (diphenyl(2-pyridinyl)phosphine (PyPPh2) and its N-heterocyclic analogues) form binuclear charged or neutral complexes with two bridged molecules of ligand in “head-to-tail” arrangement.32,47−49,53,54 As a rule, these complexes demonstrate luminescence with emission maxima in the range of blue to yellowish-green color of the visible spectrum (λem of ca. 370−500 nm).27,32,47−49,53,55,56 Herein we present the detailed report concerning the synthesis and characterization of a series of charged binuclear silver(I) complexes based on pyridylphospholanes, and their unique solid-state NIR luminescence at room temperature.

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RESULTS AND DISCUSSION Synthesis and Structural Characterization. Phospholanes 1−3 bearing pyridyl substituents on the phosphorus atom were synthesized according to the recently reported procedure.57 Reaction of ligands 1−3 and silver(I) tetrafluoroborate in a 1:1 ligand-to-metal ratio in dichloromethane or in acetonitrile led to the formation of binuclear complexes 4−6 (Scheme 1) (for experimental details see Supporting Information). Scheme 1. Synthesis of Complexes 4−6

The NMR (Figures S1−S6) and IR spectroscopy, mass spectrometry, and elemental analysis data of 4−6 revealed the formation of binuclear P,N-coordinated complex with [L2Ag2](BF4)2 composition. In spite of the photosensitivity of silver(I) compounds, complexes 4−6 demonstrated good stability at ambient conditions and no photodestruction occurred for several months. In particular, no degradation under UVirradiation was observed. The solid-state IR spectra of compounds 4−6 in KBr pellets show vibrational bands at 521 (m), 765 (m), 1068 (s) cm−1 (4); 521 (m), 766 (w), 1055 (s) cm−1 (5); 520 (m), 764 (w), 1053 (s) cm−1 (6) (Figures S7−S12), assigned to the tetrafluoroborate anion. According to Nakamoto,58 the isolated BF4− anion of Td symmetry possesses four normal modes of vibration (769, ν1; 353, ν2; 984/1016, ν3; 524/529, ν4, for 11BF4− /10BF4−), with only two of them (ν3 and ν4) being infrared active. Coordination of the BF4− anion lowers the symmetry, splitting the ν3 and ν4 into two components. The previously infrared-inactive modes ν1 and ν2 B


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Inorganic Chemistry

PXRD patterns of complexes 4−6 demonstrate good agreement with single-crystal XRD data and provide evidence of the homogeneity of the samples (Figures S15−S17). Photophysical Properties and Characterization. Complexes 4−6 in acetonitrile solutions weakly emit in the blue region of the visible spectrum (378−416 nm) (Figure S18, Table 1) upon excitation at 309−328 nm (Figure S18). Similar emission bands were observed in DMSO solutions (Figure S20). Freezing of the solutions leads to a bathochromic shift of the emission maxima by 70−100 nm (Figure S2). The luminescent behavior of 4−6 in acetonitrile solutions at room temperature is similar to that of the previously described binuclear silver(I) complexes based on P,N-ligands, phosphines, or N-heteroaromatic ligands, which usually emit at the range ca. 400−550 nm.47,53,60,61 The experimental data are in agreement with quantum chemical computations. TD-DFT computed (see Supporting Information for details) energy of the vertical transition from the first triplet excited-state T1 to the ground-state S0 of the cationic part of complex 4 amounts to 3.01 eV, which corresponds to the emission wavelength of 412 nm. These values match the experimental emission characteristics, 3.28 eV and 378 nm, respectively, of complex 4 in acetonitrile solution (Table 1). The highest occupied molecular orbital (HOMO) computed for the S0 state on the optimized T1 state geometry is localized mostly at Ag+ ions and P atoms, whereas the lowest unoccupied molecular orbital (LUMO) is mostly contributed by pyridyl moieties, however, with participation of Ag atomic orbitals (Figure S21 and Table S1, Supporting Information). Thus, the emission is of mixed 3MLCT and intraligand chargetransfer (3ILCT) character. In comparison to common photophysical behavior of Ag(I) complexes in solutions, complexes 4−6 demonstrate an unusual solid-state NIR luminescence with emission maxima at 765−902 nm, i.e., at the tissue penetration region (Figure 2, see Figure S22 for solid-state excitation spectra) with a quantum yield of about 1% at room temperature. The Stokes shift of the observed emission maxima of 4−6 and excited-state lifetimes in the microsecond domain indicate the triplet origin of the observed emission (Table 1). The decay kinetics for 4−6 are two-exponential ones with two lifetime values. Non-monoexponential behavior of decay curves is most probably associated with nonradiative processes.62−64 The Stokes shift values are very large and comparable to those of a NIR luminescent Pt-metalloporphyrin complex,65 a gold−sulfur cube,66 gold−selenide clusters,67 and copper(I) complexes.68 Such an abnormally large Stokes shift may suggest that the excited-state structure is highly distorted from that of the ground state.69 The quantum yield efficiencies of 4−6 are comparable to those of d10 transitionmetal compounds.68 We hypothesize that such dramatic differences in the luminescence of 4−6 in solution and in the solid state arise

Figure 1. ORTEP diagram showing 50% probability anisotropic displacement ellipsoids of non-hydrogen atoms for the cationic parts of compounds 4−6 according to single-crystal X-ray diffraction data. BF4− counterions are omitted for clarity. Selected interatomic distances (Å) for 4: P1−C1 1.825(4), N1−C1 1.349(5); for 5: P1−C1 1.840(3), N1−C1 1.348(5); for 6: P1−C1 1.853(6), N1−C1 1.341(8). Equivalent atoms are labeled by the sign i: symmetry operation (1 − x, 1 − y, 1 − z) for 4 and 6, symmetry operation (2 − x, 1 − y, 1 − z) for 5.

characterized by the presence of the intermolecular π−π interactions between pairs of pyridyl moieties (symmetry operation (1 − x, 1 − y, 1 − z)) with an angle of 0.00(4)°, centroid−centroid distance of 3.793(3) Å, and shift distance of 0.925(6) Å. Tight placement of the cationic parts and tetrafluoroborate anions is a common feature in the crystal structure of complexes 4−6 (Figure S14). The Kitaigorodsky packing index (percent of the filled space) of 4, 5, and 6 is equal to 71.1%, 71.7%, and 71.6%, respectively, that reveals the dense crystal packing of the complexes. The experimental Table 1. Photophysical Data of 4−6 4 5 6

λabs,a nm

λexc,a nm

λem,a nm

τ,a μs (contrib %)

λexc,b nm

λem,b nm

270, 426 298, 435 276, 444

335 365 395

765 808 902

0.31 (13.5), 2.01 (86.5) 0.31 (12.9), 2.1 (87.1) 0.19 (15.4), 1.07 (84.6)

328 328 309

378 433 416

a Measurements provided for the solid-state samples at 273 K. bMeasurements provided for the acetonitrile solutions (2.7 × 10−5 mol L−1) at 273 K.

C


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Inorganic Chemistry

methylbenzimidazole diphenylphosphines,75 pyridyl-containing triazoles,76 and terpyridines77) demonstrate blue or green emission. Thus, we can hypothesize that there are some requirements in addition to the dense crystal packing, which can be essential for IR luminescence, i.e., the coordination of metal center to both phosphine and pyridyl (or its̀ Nheterocycle analogues) groups, Ag···Ag metallophilic interactions, and the presence of BF4 anion.

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CONCLUSIONS In summary, we have synthesized a series of binuclear silver(I) complexes with pyridyl-containing phospholanes, which demonstrate the unique solid-state NIR luminescence with emission maxima in the range 765−902 nm. Quantum chemical computations and analysis of the crystal structures of 4−6 suggest that the observed NIR luminescence of complexes 4−6 in the solid state is mainly due to the effects of crystal packing which results from tight placement of the cationic parts and tetrafluoroborate anions. This hypothesis is confirmed by photophysical experiments in acetonitrile solutions, which demonstrated that complexes 4−6 in the solutions emit at ca. 440 nm. A convenient synthetic route, exceptional luminescent properties, and good stability under ambient conditions of the obtained complexes could provide further practical application. Further exploration in this field is in progress in our group.

Figure 2. Solid-state emission spectra of complexes 4−6 recorded at 298 K.

from densely packed crystals of complexes that promote intermolecular interactions, particularly from the formation of an infinite chain for compound 4 or from π−π interactions between pairs of pyridyl moieties for compound 5’s tight placement of cations and anions. Quantum chemical computations based on the X-ray structures taken without optimization predict the lowest-energy transition at 339 nm for the isolated cationic part of complex 4 (Figure 1); at 355 nm for the neutral complex 4 molecule, when two [BF4]− counterions are taken into account; and at 372 nm for the trimer of complex 4 molecules (Figure S23). This trend suggests that the bathochromic shift of the lowest-energy absorption band arises from intermolecular interactions in densely packed crystals of complexes 4−6. (See Figure S24 for experimental UV spectra.) Earlier similar dependence was observed for luminescent one-dimensional coordination polymer {[Ag2(PhPPy2)2Cl](ClO4)}n (λem = 520 nm, solid state, room temperature).66 Bathochromic effects for absorption maxima of {[Ag2(PhPPy2)2Cl](ClO4)}n were obtained when electronic absorption spectra for mono-, di-, and trimeric units of polymer were computed. The trend predicted for the absorption spectra should also be expected for the emission spectra. According to our computations for complex 4, the lowest-energy absorptions correspond to transitions from the HOMO to the LUMO, with the former being mostly contributed by the atomic orbitals of Ag+ ions, whereas the latter is localized on pyridyl rings (Figure S25). Thus, these bands belong to metal-toligand charge-transfer transitions (1MLCT). The nature of the solid-state emission of the obtained binuclear silver(I) complexes is not entirely clear, although the red shift of emission maxima in the solid state relative to solutions appears to be mainly due to dense crystal packing, similar to the cases observed for coordination polymers70 as well as for organic polymeric luminophores 7 1 and 2-(diethylamino)cinchomeronic dinitrile derivatives.72 At the same time complex [Ag2(PyPPh2)2](OTf)2 with dense crystal packing (the Kitaigorodsky packing index of 70.2%) is described as blue-emissive (λem 497 nm), suggesting the importance of the presence of the tetrafluoroborate anion. A number of similar binuclear silver(I) complexes with tetrafluoroborate anion bearing different ligands (dppm,73 or dppm-based,74 1-

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b03474. Detailed experimental and computational procedures, structures of compounds, and characterization data including powder X-ray diffraction, IR spectra, and crystallographic information (PDF) Accession Codes

CCDC 1862201−1862203 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Aliia V. Shamsieva: 0000-0002-8056-1523 Elvira I. Musina: 0000-0003-3187-8652 Robert R. Fayzullin: 0000-0002-3740-9833 Ilya E. Kolesnikov: 0000-0002-5051-4064 Sergey A. Katsyuba: 0000-0001-9196-9308 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Syntheses and characterizations of complexes 4−6 were carried out as part of the research project of the Russian Foundation for Basic Research No. 18-33-00190 mol_a. The structure determination and computational procedures were carried out D


Article

Inorganic Chemistry with the financial support from the government assignment for FRC Kazan Scientific Center of RAS. The photophysical measurements were carried out using equipment from the Center for Optical and Laser Materials Research of St. Petersburg State University. The authors gratefully acknowledge the CSF-SAC FRC KSC RAS for the registration of infrared spectra and NMR spectra, ESI, and diffraction data.

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