Chemical Volume 10 Number 18 14 May 2019 Pages 4717–4932 Science rsc.li/chemical-science ISSN 2041-6539 EDGE ARTICLE Peter W. Roesky et al. Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed fl uorescence Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed Cite this: Chem. Sci.,2019,10,4742 fl † All publication charges for this article uorescence have been paid for by the Royal Society a a a a of Chemistry Thomas J. Feuerstein, ‡ Bhupendra Goswami,‡ Pascal Rauthe, Ralf Koppe,¨ Sergei Lebedkin,b Manfred M. Kappesbc and Peter W. Roesky *a The enantiomerically pure ligand P,P-diphenyl-N,N0-bis((R)-1-phenylethyl)phosphinimidic amide (1; (R)- HPEPIA) was synthesized and subsequently deprotonated with alkali metal precursors to yield dimeric complexes [M2{(R)-PEPIA}2](M¼ Li (2), Na (3), K (4), Rb (5)). The cesium compound [M{(R)-PEPIA}] (6) crystallized as a cocrystal composed of dimeric ([Cs2{(R)-PEPIA}2](6d) and 1D-polymeric ([Cs{(R)- PEPIA}]n)(6p) species in a 1 : 1 ratio. The coordination polymer 6p features a unique sinus-shaped configuration of repeating –Cs–N–P–N–Cs–N–P–N– units. Unusual photoluminescence (PL) properties were found for solid 1–6: in contrast to the fluorescent ligand 1, the alkali metal complexes Creative Commons Attribution 3.0 Unported Licence. show phosphorescence at low temperatures (<100 K) and thermally activated delayed fluorescence (TADF) above 150 K. The latter provides for PL quantum yields up to 36% (3) at ambient temperature. Received 4th February 2019 DFT calculations support that both 1 and 2–6 have similar singlet and triplet excited states with energy Accepted 11th March 2019 d separations of a few tens of meV. The strongly enhanced intersystem crossing (ISC) in the metal DOI: 10.1039/c9sc00629j complexes, resulting in TADF, is attributed to their dimeric structure. This suggests that the fluorophore rsc.li/chemical-science dimerization may serve as a tool to effect ISC for the design of TADF emitters. Introduction alkali metals and other elements,11,12 which are dealing with This article is licensed under a achiral versions of iminophosphonamides. However, the In coordination chemistry, mono anionic chelating nitrogen chemistry with chiral iminophosphonamide ligands is still donor ligands such as b-ketiminates,1 aminotroponimates2 nearly dormant. In 2007, racemic trans-1,2-diaminocyclohexyl- 3 4 linked N-aryl bis(iminophosphonamines) and subsequent Open Access Article. Published on 09 Elba 2019. Downloaded 25/09/2021 7:43:23 PM. bis(phosphinimino)methanides, amidinates and closely related guanidinates4f,4h,5 have been widely used to stabilize complexes with group 3 and group 13 elements were reported by 13 metal complexes.6 Among these ligands, NXN type donor Hill et al. More recently, Li and Guan reported on yttrium and ligands are particularly versatile because of their ability to alkaline earth metal complexes of chiral iminophosphonamides stabilize metal complexes by pincer-type coordination to form and their application as catalysts in cross-dehydrogenative 14 four-membered metallacycles. Furthermore, ne tuning of the coupling reactions of amines. In both reports, the chiral donor properties of NXN ligands by varying X {e.g., X ¼ BR center was solely introduced at one nitrogen atom of the NPN (boraamidinate),7 CR (amidinate),4a–e N (triazenide),8 SR (sul- ligand. To the best of our knowledge, chiral iminophosphona- 9 10 11 namidinate) and PR2 (iminophosphonamide)} is possible. mides bearing chiral centers at both nitrogen atoms have not The iminophosphonamides (NPN) having the general formula been known up to now. Moreover, there have been no reports on 0 À [R2P(NR )2] can be considered as the nitrogen analogues of chiral alkali metal iminophosphonamides. phosphinate anions, in which oxygen atoms are replaced by two Recently, we described the chiral version of an amidinate 15 amide groups. There are many reports on the complexes of ligand bearing chiral centers on both nitrogen atoms, and its rare earth metal complexes which served as suitable catalysts 16 aInstitute for Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. for the asymmetric intramolecular hydroamination, as well as 17 15, 76131 Karlsruhe, Germany. E-mail: [email protected] for the ring opening polymerisation of rac-lactide. These bInstitute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von- results directed our attention to the synthesis of a chiral version Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany of an iminophosphonamide ligand, since this would show cInstitute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber- distinct structural (and complexation) features in comparison Weg. 2, 76131 Karlsruhe, Germany with amidinate ligands. Indeed, the commonly observed X–N † Electronic supplementary information (ESI) available. CCDC 1892950–1892955. bond length for amidinates (X ¼ CR) is 1.33 A˚ as compared to For ESI and crystallographic data in CIF or other electronic format see DOI: ˚ ¼ 10.1039/c9sc00629j 1.60 A in the case of iminophosphonamides (X PR2). As – – ‡ These authors contributed equally. a result, the latter ligands show wider N M N bite angles, 4742 | Chem. Sci.,2019,10,4742–4749 This journal is © The Royal Society of Chemistry 2019 View Article Online Edge Article Chemical Science where M is the coordinated metal atom. Furthermore, they In consistence, six signals were detected in the 13C{1H} NMR d ¼ exhibit a higher steric demand in the backbone, due to the spectrum in pairs for the CH3 ( (C6D6) 30.8, 25.9 ppm), CH d ¼ central quaternary P atom. ( (C6D6) 54.1, 49.9 ppm) and benzyl ipso-Cq carbon atoms 0 d ¼ Herein, we report on the synthesis of P,P-diphenyl-N,N - ( (C6D6) 152.7, 146.6 ppm). Furthermore, the NH proton was bis((R)-1-phenylethyl)phosphinimidic amide (1; (R)-HPEPIA) – observed as a broad singlet at 2.70 ppm in the 1H NMR spec- the rst enantiopure iminophosphonamide with chiral trum. In the FT-IR spectrum of 1 the corresponding NH À substituents at both nitrogen atoms. Subsequent deprotonation stretching mode was found at 3362 cm 1. Colorless single with common precursors of alkali metals led to the dimeric crystals of 1, suitable for X-ray structure analysis, were grown alkali metal derivatives. Investigation of their photo- from n-heptane. Compound 1 crystallizes solvent-free in the luminescence (PL) properties in the solid state supported by monoclinic chiral space group P21 with four molecular entities DFT calculations revealed a quite interesting behavior. The in the asymmetric unit cell (Fig. 1). The P1–N1 bond length of alkali metal compounds show bright PL which is contributed by 1.682(3) A˚ is in the range for a P–N single bond, while the P1–N2 phosphorescence at low temperatures and thermally activated bond length of 1.561(3) A˚ is in the range of a P–N double bond, delayed uorescence (TADF) above 150 K. Small (metallo) therefore the hydrogen atom was clearly assigned to the organic molecules, which exhibit TADF have recently attracted nitrogen atom N1. The N1–P1–N2 angle of 121.6(2) is compa- special attention because of their application potential for rable to that in similar compounds.10 organic light-emitting diodes.18 Their advantage lies in the fact Subsequently, we deprotonated the enantiopure ligand (R)- 1 that the TADF mechanism allows in principle for PL quantum HPEPIA ( ) and obtained the dimeric compounds [M2{(R)- ¼ 2 3 4 5 yields approaching 100%, due to fast intersystem crossing (ISC) PEPIA}2](M Li ( ), Na ( ), K ( ), Rb ( )) and [Cs2{(R)- 6 between singlet (S1) and triplet (T1) excited states with close PEPIA}2]/[Cs{(R)-PEPIA}]n ( ) using the common alkali metal 19 energy levels. To the best of our knowledge, this is the rst precursors n-BuLi, NaH, KH, and MN(SiMe3)2 (M ¼ Rb, Cs) example of TADF emitters based on the iminophosphonamide (Scheme 2). The synthesis of 5 and 6 could also be performed 1 Creative Commons Attribution 3.0 Unported Licence. derivatives. The fast ISC in these compounds is attributed to directly with elemental Rb and Cs (Scheme 2). In contrast to , their dimeric structure facilitating intramolecular charge sharp signals with well resolved ne couplings were observed transfer upon photoexcitation.20 The pronounced effect of the for the alkali salts 2–6 in the 1H NMR spectra. The CH proton 3 uorophore dimerization on the ISC parameters may be useful was detected as a doublet of quartets due to JPH coupling for the design of other efficient TADF materials. (conrmed by 1H{31P} NMR) across the nitrogen and phos- 3 phorousatoms,aswellasdueto JHH coupling with the CH3 protons. The absence of the NH proton in the 1H NMR spectra Results and discussion along with the lack of a NH stretching mode in the FT-IR Synthesis and characterization spectra indicate full deprotonation of the ligand in all This article is licensed under a compounds. For compounds 3–6 only one singlet was 0 The enantiopure ligand P,P-diphenyl-N,N -bis((R)-1-phenylethyl) observed in the 31P{1H} NMR spectra. 1 phosphinimidic amide ( , (R)-HPEPIA) was synthesized in In contrast, the 31P{1H} NMR spectrum of compound 2 a Staudinger reaction from the known compounds (R)-a-meth- 2 Open Access Article. Published on 09 Elba 2019. Downloaded 25/09/2021 7:43:23 PM. showed a pseudo-quartet, which was assigned to JPLi coupling 21 22 ylbenzyl azide and HN(R-CHMePh)(PPh2) (Scheme 1). The NMR spectrum of 1 is complex and strongly solvent dependent, which apparently results from (E)/(Z) isomerization and tautomerization (Scheme 1). In the 1H NMR spectrum broad signals without ne coupling were observed, similar to the results for the methylbenzyl substituted amidine (R,R)-N,N- 15 bis-(1-phenylethyl)benzamidine.