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The peculiarities of complex formation and energy transfer

processes in lanthanide complexes with

2-(tosylamino)benzylidene-N-benzoylhydrazone

Anton D. Kovalenkoa, Ivan S. Bushmarinovb, Anatolii S. Burlovc,

Leonid S. Lepnevd, Elena G. Ilinae, and Valentina V. Utochnikovaa,d

a M. V. Lomonosov Moscow State University

Leninskiye Gory 1-3, Moscow, Russian Federation 119991

b A. N. Nesmeyanov Institute of Organoelement Compounds

Russian Academy of Sciences, Vavilova St. 28, Moscow, Russian Federation

119991

c Institute of Physical and Organic Chemistry

Southern Federal University, Stachki Ave. 194/2, Rostov-on-Don, Russian

Federation 344090

d P. N. Lebedev Physical Institute, Russian Academy of Sciences

Leninskiy Prospekt 53, Moscow, Russian Federation 119991

e Altai State University

61 Lenina, Barnaul, Russian Federation 656049

Abstract: Depending on the local excess of lanthanide ion (Ln = Lu, Yb, Er, Dy,

Tb, Gd, Eu, Nd) or 2-(tosylamino)-benzylidene-N-benzoylhydrazone (H2L),

lanthanide complexes, containing either mono-deprotonated ligand (Ln(HL)2X, X

= Cl, NO3) or both mono- and dideprotonated ligands (Ln(L)(HL)) were

preparatively obtained. The crystal structures of Lu(HL)2Cl, Yb(L)(HL)(H2O)2,

Yb(L)(HL)(EtOH)2(H2O) and Er(L)(HL), determined by single crystal diffraction

data or from powder diffraction data using Rietveld refinement, have shown the

surprising resemblance. The studying of luminescence temperature dependence of

Eu(HL)2Cl and Eu(L)(HL) showed that europium luminescence is quenched by

thermally-activated 5D0→T1 energy transfer. The luminescent thermometers based

on these complexes demonstrated the sensitivity up to 7.7% at 85K which is the

highest value above liquid-nitrogen temperatures obtained to date.

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2018

Absorption spectroscopy

Absorption spectra of the lanthanide complexes in DMSO solution were obtained using single-

beam spectrophotometer SF-2000 (OKB Spectr) (l = 10.0 mm) in the range 250-1000 nm.

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25000

30000

35000

40000Eu(L)(HL)

Yb(L)(HL)

(c

m-1M

-1)

Wavelength (nm)

Figure 1 Absorption spectrum of Eu(L)(HL) in DMSO

Diffuse reflection spectroscopy

Diffuse refection spectra were recoded using Perkin Elmer LAMBDA 950 spectrometer in the

range 200 – 1150 nm.

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(1-R

)2

2R

Wavelength (nm)

Yb(HL)2Cl

Figure 2 The DR spectrum of Yb(HL)2Cl

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1,2

1,4 Yb(L)(HL)

(1-R

)2

2R

Wavelength (nm)

Figure 3 The DR spectrum of Yb(L)(HL)

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(Yb-Lu)(L)(HL)

(Yb-Gd)(L)(HL)

No

rma

lize

d(1

-R)2

2R

Figure 4 The difference between normalized DR spectra of Yb(L)(HL) and Lu(L)(HL), Gd(L)(HL)

400 500 600 700 800

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1,0

Wavelength (nm)

(Yb-Lu)(HL)2Cl

No

rma

lize

d(1

-R)2

2R

Figure 5 The difference between normalized DR spectra of Yb(HL)2Cl and Lu(HL)2Cl

Crystallographic data

The single crystal measurements were performed on Bruker APEX II (Mo radiation) and Bruker

APEX II DUO (Cu radiation, microfocus source, used for Yb(L)(HL)(EtOH)2(H2O)) CCD

diffractometers. All single crystal structures were solved using SHELXT [1] and refined using

SHELXL [2,3].

Structure for Er(L)(HL) was determined form powder data. The diffraction pattern was collected

using Cu Kα1 radiation on a Bruker D8 Advance Vario powder diffractometer equipped with a

Ge(111) monochromator and a LynxEye 1D silicon strip detector. The powder pattern was

indexed using the SVD-Index algorithm[4] as implemented in TOPAS 5[5]. The structure was

solved by Parallel Tempering as implemented in FOX[6] using two rigid bodies with torsions

allowed to vary, one corresponding to a free ligand and the other consisting of a ligand linked by

two nitrogen atoms to the metal atom. Further refinement was carried out in TOPAS 5, with

restraints on all covalent bonds and bond angles between non-metal atoms. A weighting scheme

by Toraya[7] with e=3.5 was used during refinement for optimal treatment of weaker reflections.

The refinement was restraint-consistent[8] with half uncertainty window HUW=0.08(4)

indicating a highly reliable structural model.

The final refined unit cell parameters and refinement indicators for Er(L)(HL) at K1 = 8 (root

mean square deviation from restraints on bond lengths of 0.0054 Å) are as follows Ошибка!

Источник ссылки не найден.: C42H35ErN6O6S2 (M =951.16 g/mol): monoclinic, space group

P21/c (no. 14), a = 18.8998(3) Å, b = 9.85077(15) Å, c = 25.1072(4) Å, β = 122.4174(9)°, V =

3945.95(11) Å3, 𝑅𝑤𝑝 = 3.44%, 𝑅𝑤𝑝′ = 5.10 %, 𝑅𝑝 = 3.49%, 𝑅𝑝

′ = 4.31 %, RBragg = 2.30%.

Figure 6 The Rietveld fit for Er(L)(HL).

Table 1. Crystal data and structure refinement for Lu(HL)2Cl, Er(L)(HL), Yb(L)(HL)(C2H5OH)2(H2O), Yb(L)(HL)(H2O)2. Identification code Lu(HL)2Cl Er(L)(HL) Yb(L)(HL)(C2H5OH)2(H2O) Yb(L)(HL)(H2O)2

Empirical formula C42H36ClN6O6S2Yb C42H35ErN6O6S2 C46H49N6O9S2Yb C42H39N6O8S2Yb

Formula weight 993.38 951.16 1067.07 992.95

Temperature/K 120 298 120 100

Crystal system triclinic monoclynic triclinic triclinic

Space group P-1 P21/c P-1 P-1

a/Å 10.6091(7) 18.90072 10.7608(6) 12.530(3)

b/Å 11.4231(7) 9.851312 12.5093(7) 15.640(3)

c/Å 17.4138(11) 25.10557 17.4399(10) 22.612(5)

α/° 87.312(2) 90 77.5710(10) 103.12(3)

β/° 73.030(2) 122.4146 83.1210(10) 101.74(3)

γ/° 85.7230(10) 90 75.2430(10) 93.34(3)

Volume/Å3 2012.1(2) 3946.239 2211.7(2) 4200.2(16)

Z 2 4 2 4

ρcalcg/cm3 1.640 1.601 1.602 1.570

μ/mm-1 2.551 5.368 2.273 5.544

F(000) 994.0 - 1082.0 1996.0

Crystal size/mm3 0.21 × 0.2 × 0.15 - 0.13 × 0.12 × 0.1 0.06 × 0.05 × 0.04

Radiation MoKα (λ = 0.71073) CuKα~1~ (λ = 1.540596) MoKα (λ = 0.71073) CuKα (λ = 1.54178)

2Θ range for data collection/° 3.576 to 52.742 - 3.788 to 56.562 4.116 to 135.786

Index ranges -13 ≤ h ≤ 13, -13 ≤ k ≤ 14, -21 ≤ l ≤ 21 - -14 ≤ h ≤ 14, -16 ≤ k ≤ 16, -23 ≤ l ≤ 23 -14 ≤ h ≤ 12, -18 ≤ k ≤ 18, -27 ≤ l ≤ 25

Reflections collected 20050 - 26258 42661

Independent reflections 8227 [Rint = 0.0546, Rsigma = 0.0775] - 10988 [Rint = 0.0630, Rsigma = 0.0900] 14318 [Rint = 0.0621, Rsigma = 0.0651]

Data/restraints/parameters 8227/2/533 - 10988/3/597 14318/160/1121

Goodness-of-fit on F2 1.045 - 0.984 1.027

Final R indexes [I>=2σ (I)] R1 = 0.0447, wR2 = 0.0804 - R1 = 0.0431, wR2 = 0.0806 R1 = 0.0620, wR2 = 0.1558

Final R indexes [all data] R1 = 0.0651, wR2 = 0.0874 - R1 = 0.0618, wR2 = 0.0859 R1 = 0.0929, wR2 = 0.1757

Largest diff. peak/hole / e Å-3 1.77/-1.14 - 1.55/-1.25 2.36/-0.63

Thermal analysis

Thermal analysis was carried out on a thermoanalyzer STA 409 PC Luxx (NETZSCH,

Germany) in the temperature range of 20-1000 oC in argon atmosphere, heating rate 10 o/min.

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We

igh

t lo

ss

Temperature (oС)

Ln2O

3

Eu(HL)2(NO

3)

Yb(HL)(L)

Nd(HL)2Cl

Er(HL)2Cl

Yb(HL)2Cl

Figure 7 Thermal analysis of the complexes

XRD powder diffraction patterns

X-ray powder diffraction (XRD) measurements were performed on a Rigaku D/MAX 2500

diffractometer in the 2θ range 5–80° with Cu Kα radiation (λ = 1.54046 Å) and on a Bruker D8

Advance diffractometer (Vario geometry) equipped with a Cu Kα1 Ge(111) focusing

monochromator and a LynxEye one-dimensional position-sensitive detector. The powder X-ray

diffraction patterns were indexed using TOPAS 5.0 software.

Figure 8 XRD patterns of Lu(L)(HL)

Figure 9 XRD patterns of Yb(L)(HL). The sample was not grinned that leaded to the preferential crystals orientations.

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Figure 10 XRD patterns of Er(L)(HL)

Figure 11 XRS patterns of Tb(L)(HL)

Figure 12 XRD patterns of Gd(L)(HL)

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Figure 13 XRD patterns of Eu(L)(HL)

Figure 14 XRD patterns of Lu(HL)2Cl

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Figure 15 XRD patterns of Yb(HL)2Cl

Figure 16 XRS patterns of Er(HL)2Cl. Contains impurities of KCl.

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Sylvine 12.97 %

Figure 17 XRD patterns of Tb(HL)2Cl

Figure 18 XRD patterns of Eu(HL)2Cl

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Figure 19 XRD patterns of Nd(HL)2Cl

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Integration of europium luminescence

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0

7F

3

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4

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nsity (

coun

ts p

er

second

)

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5D

0

7F

2

Figure 20 The integration of europium luminescence in the luminescence spectra of Eu(HL)2Cl at 167K. The bold curve is

complex luminescence, the red curve is fitting of the organic luminescence.

The organic part of luminescence was fitted with B-spline function. The bands of 5D0→7FJ (J =

1–4) transitions were integrated with the fitted organic luminescence as a baseline (see Figure 20

as an example) and summarized to give the integrated europium luminescence intensity. The

same procedure was run for the spectra of Eu(L)(HL) in the range 77-200 K and Eu(HL)2Cl in

the range 77-240 K, where europium luminesce could still be observed. The integration were

made using Origin Pro 9.0 software.

IR spectroscopy

IR spectra in the ATR mode were recorded on a spectrometer SpectrumOne (Perkin-Elmer) in

the region of 400-4000 cm-1.

3600 3200 2800 1600 1400 1200 1000 800 600

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Tra

nsm

issio

n (

%)

Wavenumber (cm-1)

Lu(HL)2(NO

3)

Lu(HL)(L)

Yb(HL)2Cl

Er(HL)2Cl

Figure 21 The IR spectra of the complexes

Luminescence spectra with time delay

Luminescence spectra with time delay were measured using Fluorolog 3 spectrofluorometer.

450 500 550 600 650 700 750

0

1

T1(L2–

)S0

Gd(L)(HL)

No delay

Time delay 30 µs

No

rma

lize

d I

nte

nsity

Wavelength (nm)

Figure 22 The luminescence spectra of Gd(L)(HL) in powder at 77K without time delay (black) and with 50 µs time delay

(red)

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0

1 T1(HL–)S

0

Norm

aliz

ed Inte

nsity

Wavelength (nm)

Gd(HL)2(NO

3)

No delay

Time delay 30 µs

Figure 23 The luminescence spectra of Gd(HL)2(NO3) in powder at 77K without time delay (black) and with 30 µs time

delay (red)

The coordination environment of lanthanide ion

a) b) c) d)

Figure 24 The coordination environment of metal ion in a) Lu(HL)2Cl, b) Er(L)(HL), c) Yb(L)(HL)(EtOH)2(H2O), d)

Yb(L)(HL)(H2O)2. Oxygen atoms are red, nitrogen atoms are blue.

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