Manganese(II) Thiocyanate Complexes with Bis(phosphine Oxide) Ligands: Synthesis and Excitation Wavelength-Dependent Multicolor Luminescence

Article abstract of DOI:10.1002/ejic.201901213

First examples of luminescent Mn^II thiocyanate complexes are presented. A series of such compounds has been synthesized via the reaction of Mn(NCS)₂ with bis(phosphine oxides), Ph₂P(O)–X–(O)PPh₂, where X = CH₂ (L1), CH₂CH₂ (L2), CH₂CH₂CH₂ (L3), CH₂C(=CH₂)CH₂ (L4), C(=CH₂)C(=CH₂) (L5) and C≡C (L6). The L1, L3 and L4 ligands, when reacted with Mn(NCS)₂ on air (EtOH/acetone, r.t.), produce chelate complexes [Mn^II(O^{^}O)₂(NCS)₂]. Under similar conditions, L5 gives ionic complex [Mn^II(L5)₃][Mn^II(NCS)₄], whereas L6 affords chain coordination polymer (CP) [Mn^II(L6)₂(NCS)₂]_n. By contrast, ligand L2 results in formation of mixed-valent chain CP [Mn^IIMn^III(L2)₃(NCS)₅]_n. Complex [Mn(L4)₂(NCS)₂] and CP [Mn(L6)₂(NCS)₂]_n display unique dual luminescence, i.e. the intraligand fluorescence (blue band) and Mn^II-centered phosphorescence (red band), the ratio of which is largely modulated by excitation wavelength. Through this feature, the luminescence color of these complexes can be smoothly tuned from deep-blue to red. Complex [Mn(L5)₃][Mn(NCS)₄] shows Mn^II-based phosphorescence only.

Full text of DOI:10.1002/ejic.201901213

A Journal of
Accepted Article
Title: Manganese(II) thiocyanate complexes with bis(phosphine
oxide) ligands: synthesis and excitation wavelength-dependent
multicolor luminescence
Authors: Maria Davydova, Irina Bauer, Valery Brel, Mariana
Rakhmanova, Irina Bagryanskaya, and Alexander V. Artem'ev
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content of this Accepted Article.
To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201901213
Link to VoR: http://dx.doi.org/10.1002/ejic.201901213

European Journal of Inorganic Chemistry
10.1002/ejic.201901213
FULL PAPER
DOI: 10.1002/ejic.200
Manganese(II) thiocyanate complexes with bis(phosphine oxide) ligands: synthesis
and excitation wavelength-dependent multicolor luminescence
[a]
[a,b]
[с]
[a,b]
Maria P. Davydova, Irina A. Bauer,
Bagryanskaya,
Valery K. Brel, Mariana I. Rakhmanova,
Irina Yu.
[b,d]
[a,b]
and Alexander V. Artem’ev*
Keywords: Phosphine oxide ligands/ Manganese / Thiocyanates / Multicolor Luminescence / Excitation dependent emission
II
First examples of luminescent Mn thiocyanate complexes are presented. Complex [Mn(L4)
2
(NCS)
2
] and CP [Mn(L6)
2
(NCS)
2
]
n
A series of such compounds has been synthesized via the reaction of display unique dual luminescence, i.e. the intraligand
II
Mn(NCS)
CH (L1), CH
C(=CH )C(=CH
reacted with Mn(NCS)
2
with bis(phosphine oxides), Ph
CH (L2), CH CH CH (L3), CH
) (L5) and C≡C (L6). The L1, L3 and L4 ligands, when excitation wavelength. Through this feature, the
on air (EtOH/acetone, r.t.), produce chelate luminescence color of these complexes can be smoothly
(NCS) ]. Under similar conditions, L5 gives tuned from deep-blue to red. Complex
] shows Mn -based phosphorescence
2
P(O)–X–(O)PPh
2
, where X = fluorescence (blue band) and Mn -centered phosphorescence
2
2
2
2
2
2
2
C(=CH
2
)CH (L4), (red band), the ratio of which is largely modulated by
2
2
2
2
II
complexes [Mn (O^O)
ionic complex [Mn (L5)
2
2
a
a
II
II
II
3
][Mn (NCS)
4
], whereas L6 affords chain [Mn(L5)
3 4
][Mn(NCS)
II
coordination polymer (CP) [Mn (L6)
results in formation of mixed-valent chain CP [Mn Mn (L2) (NCS) ] .
3 5 n
2
(NCS) . By contrast, ligand L2 only.
2 n
]
II
III
_
___________
Particular interest is devoted to Mn(II) halide complexes with
[
a]
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of
Russian Academy of Sciences, 3, Acad. Lavrentiev Ave., 630090
Novosibirsk, Russian Federation
E-mail: chemisufarm@yandex.ru
http://store.niic.nsc.ru/en
[25, 27-37]
phosphine oxide ligands.
Mn(Ph PO) Br ], exhibit bright photo- and triboluminescence at
ambient temperature.
derived from DPEPhos dioxide were claimed as bright photo- and
For instance, some of them, e.g.
[
3
2
2
[
27-31]
2 2
The [Mn(DPEPhosO )Hal ] complexes
[
32]
[
[
b] Novosibirsk State University, 2, Pirogova Str., 630090 Novosibirsk,
Russian Federation
c]
triboluminescent. An intriguing vapochromic luminescence was
[33]
found for 1D coordination polymer [Mn(dppeO
recently, utilizing adducts of MnCl and MnBr
bis(diphenylphosphoryl)dibenzofuran, first efficient Mn-based
2
2
)Br ]
n
.
More
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian
Academy of Sciences, 28, Vavilova Str., 119991 Moscow, Russian
Federation
2
2
with 4,6-
[
34]
PhOLEDs were fabricated.
By contrast, Mn(II) pseudohalide
[
d] N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch, Russian Academy of Sciences, 9 Lavrentiev Ave.,
complexes supported by phosphine oxide ligands remain neglected,
although they are also expected to be promising class of luminescent
materials. In particular, among such Mn(II) thiocyanate complexes,
6
30090 Novosibirsk, Russian Federation
Supporting information for this article is available on the WWW
under http://www.eurjic.org/ or from the author.
only
Mn(Ph
[Mn(Ph
four
examples
were
[(Ph PO)
and [Mn (µ-dpppO
credibly
2
described,
Mn (NCS) Mn(Ph PO)
(NCS) ](NCS)
viz.
[
38]
SCN
[39]
[
3
PO)
PO)
2
(NCS)Cl],
3
3
2
],
[
39]
.[40]
Introduction
3
4
(NCS)
2
]
2
2
)
4
2
2
To our knowledge, luminescence of any Mn thiocyanate complexes
was not studied at all. Taking this into account, as well as the rich
At present, MnII complexes and Mn -doped solids attract great
attention due to their unique photo- and electroluminescent
properties, low cost, high stability and facile processability.[1] The
luminescence of these materials is originated by spin-forbidden d–d
transitions within Mn2+ ion, has a phosphorescent character and
II
[
41]
coordination abilities of the [NCS]¯ ion, the development of new
Mn(NCS) complexes with phosphine oxide ligands is a major
2
challenge in the context of access to novel emitting materials
ranging from discrete compounds to complicated 3D frameworks.
Herein, aiming to reveal the potential of Mn thiocyanate
compounds in terms of luminescence, we have investigated a series
[
1,2]
covers the spectral range from ~500 nm to near-IR edge. Because
2
+
of a strong sensitivity of Mn -based emission to ligand field
strength and symmetry,[1-3] its energy can be controlled via changing
of the coordination geometry, whereas lifetime can be tuned by
varying nature of the ligated atoms. The classical cases are
II
II,III
of Mn and Mn
complexes synthesized through the reaction of
Mn(NCS) with a set of the bis(phosphine oxide) ligands L1–6
2
depicted in Scheme 1. Some of the resulting molecular complexes
and coordination polymers (CPs), being essentially the first
h d
represented by octahedral (O ) and tetrahedral (T ) ligand fields, in
2
+
II
which Mn ion emits in red (610–660 nm) and green (510–560 nm)
representatives of emissive Mn thiocyanate compounds, exhibit
regions, respectively.[1-3] For example, the commonly known
unique excitation wavelength-dependent dual luminescence at
ambient temperature. From this viewpoint, the designed Mn-based
dual emitting single molecule-based materials are promising
platform for creation of new optoelectronic devices such as multi-
]2− display green luminescence,
[4-15]
while
halomanganates [MnHal
the complexes of [(L)MnHal
4
3
] and L
6
[Mn
3
Cl12] type (L = protonated
and Mn -doped sulfide and oxide
exhibit red emission. The compounds containing
both tetrahedral and octahedral Mn(II) centers, e.g.
[
16-22]
2+
or alkylated N-base)
[
1, 23, 24]
[42-44]
nanocrystals
color OLEDs, luminescent sensors and photoswitches.
[
25]
[
Mn(dppeO
2
)
3
]MnHal
4
, manifest a dual emission.
Moreover,
unique thermochromic luminescence associated with conversion of
2
+
a tetrahedronal to trigonal bipyramidal geometry of Mn has been
[
26]
reported.
Submitted to the European Journal of Inorganic Chemistry
1
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European Journal of Inorganic Chemistry
10.1002/ejic.201901213
L4 react with Mn(NCS)
2
to afford neutral bis-chelating complexes
II
1
, 3 and 4 of a general formula [Mn (O^O)
2
(NCS)
2
]. Meanwhile,
ligand L5 under similar conditions provides ionic complex
II
II
[
Mn (L5)
tetrahedrally-coordinated [Mn(NCS)
ligand L6 is found to be easily assembled with Mn(NCS)
3 4
][Mn (NCS) ] (5), composed by tris-chelated cation and
2
–
4
]
anion. The acetylene-based
into 1D
2 2 n
CP [Mn (L6) (NCS) ] (5), the adjacent Mn ions of which are
2
II
2+
linked by two bridging ligands. The most surprising result is
observed with 1,2-bis(diphenylphosphinyl)ethane (L2) that forms
II
III
mixed-valent chain polymer [Mn Mn (L2)
3
(NCS)
modules separated by
bridging L2 ligands. The Mn ions within CP 2 are obviously
resulted from oxidation of Mn(NCS) on air. This distinctive feature
of L2 can tentatively be ascribed to its higher ability to stabilize
5 n
] (2). The latter
II
III
2 3
is composed of Mn (NCS) and Mn (NCS)
Scheme 1. Structures of the studied bis(phosphine oxide) ligands L1–6.
III
2
Results and Discussion
III
Mn (NCS)
3
species as compared to other tested ligands. Moreover,
Synthetic part
the basicity of thiocyanate anions can also favor the formation of
mixed valence Mn -Mn CP 2. Note that the terminal [NCS]¯
anions in compounds 1–6 act as N-bonded ones that is in the line
II
III
To disclose coordination abilities of ligands L1–6 toward
Mn(NCS) , a series of experiments has been carried out using
2
various molar ratios of the reactants. The reactions have been
performed in EtOH/acetone mixed solvent under ambient conditions
[
38,39,41]
with HSAB concept and the literature data.
note also that, apart from the titled bis(phosphine oxides),
DPEPhosO and 1,2,4,5-tetrakis(diphenylphosphinyl)benzene have
been tested in the reaction with Mn(NCS) , but no X-ray quality
crystals of products formed have been obtained.
It is relevant to
2
(
r.t., air, 1 h) with Mn(NCS)
MnCl ·4H O with NaNCS. The isolated products have been
analyzed by single crystal (sc-XRD) and powder X-ray diffraction
PXRD) techniques, which have revealed the following regularities
and peculiarities of the reaction (Scheme 2). So, ligands L1, L3 and
2
generated in situ by the reaction of
2
2
2
(
2
Scheme 2. Reactions of Mn(NCS) with bis(phosphine oxide) ligands L1–6. (Conditions: EtOH/acetone, r.t., air).
Crystal structures
Compounds 1–6 have been isolated in 47–68% yield (non-
optimized) as air- and light-stable colorless solids, soluble in MeCN
and CH Cl . Their phase purity has been validated by PXRD (Figs.
2 2
S1–6) and microanalyses data. FT-IR spectra of 1–6 in middle
region well agree with available X-ray structures, demonstrating
vibrations of the organic ligand’s skeleton (Figure S7). The
Complex 1 crystallizes from DMF as solvate 1·2DMF showing
molecular structure. The metal atom has an octahedral environment
composed of four oxygen atoms of the chelating ligands L1 and two
nitrogen atoms of [NCS]¯ groups (Fig. 1). Since the latter are
4 2
mutually adjacent within [Mn@O N ] octahedra, complex 1 can be
asymmetric stretching vibrations of the thiocyanate anions (νCN
appear as a strong band at ~ 2065–2077 cm , thus confirming their
terminal N-bonded pattern.[45]
)
considered as cis-isomer. One of the N-bonded terminal [NCS]¯
anions is roughly linear, whereas the second one is slightly bended.
The Mn–O (av. 2.206 Å) and Mn–N (av. 2.167 Å) distances are
–
1
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European Journal of Inorganic Chemistry
10.1002/ejic.201901213
comparable with those of MnII complexes.[38-40] In general, bond
positions. Note that the Mn –O bond lengths (av. 2.080 Å) are
III
II
lengths and angles in the [Mn(NCS)
2
] unit of 1 are consistent with
shorter as compared to Mn –O (av. 2.182 Å) ones. The similar trend
is observed for Mn –N (ca. 2.100–2.183 Å) and Mn –N (ca. 2.195
and 2.285 Å) distances.
III
II
those found in complexes 2–6 and in the related compounds reported
[
38,39,46-49]
earlier.
Compounds 3 and 4 reveal nearly superimposable molecular
structures (Figs. 3 and 4) that differ only by middle atom in the
ligand chains (CH versus C=CH , accordingly). In terms of
2 2
chemical bonding, both complexes resemble 1, but in contrary to the
latter, they are trans-isomers. Apparently, cis-isomers of 3 and 4 are
energetically less preferable because of a higher steric hindrance
entailed by the neighboring ligands L3 and L4. At the same time, a
smaller structure of L1 does not prevent existence of 1 in the cis-
form.
Figure 1. Molecular structure of 1·2DMF. Hydrogen atoms and solvate
molecules are omitted for clarity. Selected bond lengths (Å) and angles (°):
Mn1–N1 2.153(2), Mn1–N2 2.182(2), Mn1–O4 2.1827(13), Mn1–O1
2
1
.1873(13), Mn1–O2 2.2192(14), Mn1–O3 2.2371(14); O4–Mn1–O1
65.11(5), N2–Mn1–O2 177.49(7), N1–Mn1–O3 174.63(7).
1
D structure of CP 2 is represented by zig-zag chains built up by
II
III
alternating Mn (NCS)
O=P(Ph )CH CH (Ph )P=O linkers in a [–Mn –L2–Mn –L2–
fashion (Fig. 2). Each Mn atom is also O,O′-
chelated by one L2 ligand that completes octahedral geometry of the
2 3
and Mn (NCS) units, bridged by the
II
II
2
2
2
2
III
III
II
Mn –L2–Mn –]
n
Figure 3. Molecular structure of 3. Hydrogen atoms are omitted for clarity.
Selected bond lengths (Å) and angles (°): Mn1–O2 2.178(4), Mn1–O1
2.185(4), Mn1–N1 2.212(5); O2–Mn1–O1´ 172.97(15), N1–Mn1–N1´
179.7(3). Symmetry code: (´) –x, y, 1.5–z.
II
4 2
metal. The formed [Mn @O N ] octahedra, similar to one of 1,
adopt the cis-structure. The Mn atom evinces a trigonal
III
bipyramidal geometry with the [NCS]¯ anions being in axial
Figure 2. A fragment of the CP 2. Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and angles (°): Mn1–O 2 2.078(2), Mn1–O1 2.082(3),
Mn1–N2 2.099(4), Mn1–N1 2.152(4), Mn1–N4 2.183(4), Mn2–O5 2.157(2), Mn2–O6 2.177(2), Mn2–O3 2.188(2), Mn2–N3 2.195(3), Mn2–O4 2.207(2),
Mn2–N5 2.285(3); O2–Mn1–O1 128.34(16), O2–Mn1–N2 123.08(15), N1–Mn1–N4 170.26(18), O3–Mn2–N3 166.75(10), O6–Mn2–O4 175.05(8), O5–
Mn2–N5 179.77(10). Symmetry codes: (´) 2–x, –y, 1–z; (´´) 1–x, –1–y, 2–z.
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European Journal of Inorganic Chemistry
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Figure 5. Molecular structure of 5. Hydrogen atoms are omitted for clarity.
Selected bond lengths (Å) and angles (°): Mn1–O4 2.1311(16), Mn1–O1
2
.1395(16), Mn1–O2 2.1446(16), Mn1–O3 2.1476(16), Mn1–O6 2.1684(15),
Mn1–O5 2.1676(16), Mn2–N3 2.033(4), Mn2–N4 2.037(3), Mn2–N1
Figure 4. Molecular structure of 4. Hydrogen atoms are omitted for clarity.
Selected bond lengths (Å) and angles (°): Mn1–O2 2.1835(13), Mn1–O1
2
1
1
.051(4), Mn2–N2 2.075(4); O4–Mn1–O1 172.42(7), O2–Mn1–O3
70.44(7), O6–Mn1–O5 173.29(7), N3–Mn2–N4 104.99(16), N3–Mn2–N1
11.24(17), N4–Mn2–N1 110.78(13), N3–Mn2–N2 107.55(17), N4–Mn2–
2
1
.1990(12), Mn1–N1 2.2249(18); O2–Mn1–O1 173.44(5), N1–Mn1–N1´
79.93(9). Symmetry code: (´) 2–x, y, 0.5–z.
N2 113.23(16), N1–Mn2–N2 108.99(15).
Ionic complex 5 is formed by tris-chelated [Mn(L5)
3
]2+ cations
]2+, metal atom lies
2
–
and [Mn(NCS)
4
]
anions (Fig. 5). In [Mn(L5)
3
2
1D chains of CP 5 are assembled by repeating Mn(NCS) moieties,
O^O
O^O
in the distorted octahedral surroundings with the Mn–O distances
which are bridged by ligands L5 in a [Mn( )Mn] manner (Fig. 6).
varying from 2.131 to 2.168 Å. On the whole, geometry of the cation
2
In the formed fourteen-membered (Mn-O-P-C-C-P-O) rings, two
[
25]
is close to that of the related [Mn(L5)
3
]MnBr
anion of 5 features tetrahedral geometry of Mn atom
4
= 0.96 ). The [NCS]¯ groups are virtually linear and bonded
4
complex.
The
slightly bended P–C≡C–P fragments are mutually crossed at the
dihedral angle of –48.11°. The distance between acetylene units of
these fragments (3.891 Å) is long for appearance of the possible
transannular π–π interaction. Each Mn atom of 5 adopts a trans-
2
–
[
(
4
Mn(NCS) ]
τ
[
50]
with metal so that Mn–N–C angle is ~167.84° that is consistent with
[
51-53]
the literature data.
4 2
[Mn@O N ] octahedral geometry with two axial thiocyanate
nitrogen atoms. Again, whilst the Mn–NCS arms are little bended,
the [NCS]¯ anions are closely linear.
Figure 6. A fragment of the CP 6. Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and angles (°): Mn1–N1 2.151(4), Mn1–O2 2.192(3),
Mn1–O4 2.240(3), Mn2–O3 2.166(3), Mn2–N2 2.172(4), Mn2–O1 2.229(3); N1–Mn1–N1´ 180.0(2), O2–Mn1–O2´ 180.0, O4–Mn1–O4´´ 180.00(13), O3–
Mn2–O3´´ 180.0, N2–Mn2–N2´´ 180.0(2), O1–Mn2–O1´´ 180.00(12). Symmetry codes: (´) 2–x, 1–y, 1–z; (´´) 1–x, 1–y, 1–z.
In crystal packing of 1, 3 and 4, the closest Mn···Mn distances
11.423, 10.725 and 10.692 Å, respectively) are quite long in terms
step decomposition starts (Fig. 7). A similar pattern is also inherent
in complex 1 that is formed upon desolvation of the parent solvate
1·2DMF (ca. 170 °C). CP 2 appears to be the least stable and starts
to decompose from 140 °C. The observed mass change at this step
(Δmobs = 7.00%) corresponds to the loss of two “SCN” units from 2
(
of possible Förster resonance energy transfer (FRET) from an
photoexcited Mn2+ ion to neighboring nonexcited Mn ion.
Meanwhile, for compounds 2, 5 and 6, where these distances are
shorter than 10 Å (8.683, 9.234 and 8.968 Å), the FRET channel may
contribute to the luminescence properties.[25]
2+
(Δmcald = 6.86%). Keeping this in mind, we have assumed that the
III
stage is associated with an intramolecular reduction of Mn (NCS)
3
II
2
modules of 2 leading to Mn (NCS) ones and thiocyanogen (SCN)
2
Thermal properties
degradation products.
The TGA/DTG study evidences that compounds 3–6 are
thermally stable up to ~ 280 °C, beginning from which one- or two-
Submitted to the European Journal of Inorganic Chemistry
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European Journal of Inorganic Chemistry
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UV-Vis spectra of the compounds 4–6 dissolved in acetonitrile
are very similar showing a strong absorption band expanding from
far-UV edge to 220 nm as well as two weaker bands maximized at
~
225 and 270 nm (Fig. S8). The high-energy band has been assigned
to π–π* transitions within phenyl groups of the ligands, while the
2
+
lower-energy bands have been tentatively ascribed to Mn -centered
spin-forbidden d–d transitions.
The emission spectra of polycrystalline 4 are presented by broad
fluorescence and phosphorescence bands at ~ 420 nm and 670 nm,
accordingly. The vibronically-structured shape of the high-energy
–
1
band with ∆kav ≈ 1100 cm implies participation of the π-orbitals of
the phenyl groups of L4 in emissive transitions. Indeed, the
nanosecond order of the lifetimes determined for this band (τ
1
= 6.3
ns, τ = 176 ns) corroborates its fluorescent origin. The decay
2
kinetics of the low-energy emission band shows rather long lifetime
4
6
of 0.92 ms that is typical for spin-forbidden T
1
(G) → A
1
transitions
2
+
[1-3, 25]
in Mn ions located in octahedral ligand field.
The excitation
Figure 7. TGA and DTA curves of 1–6.
spectrum of 4 (Fig. 8a), monitored for the phosphorescence band,
2
+
features broad unresolved bands of Mn ion terms. The excitation
profile of the fluorescent band is a broad structureless band (covered
250–420 nm region) that can be arisen from π→π* transitions in
coordinated ligand L4. Note that the position and ratio of the red and
blue bands are largely modulated by excitation energy. This
excitation wavelength dependent behavior of 4 is remarkable since
it allows fine-tuning the color of the luminescence through slight
changing of the excitations. As illustrated by CIE chromaticity
diagram (Fig. 9), a gradual increase of the excitation wavelengths
from 280 to 400 nm leads to a smooth changing of the emitting light
color from red to green.
Photoluminescent properties
The photophysical measurements have revealed a weak solid-state
luminescence for compounds 4–6 at ambient temperature.
Complexes 1–3 are essentially non-emissive. However, despite the
low quantum efficiency (ΦPL of 4–6 are 1%, 2% and 1%,
respectively), complexes 4 and 6 are characterized by a unique
multicolor emission expressed by two complementing bands, the
ratio of which is sensitive to the excitation wavelength. It is relevant
to note in this regard that the Mn-based multicolor emitting materials
are still very limited,[25, 36] although they are high-demand for the
creation of low-cost white OLEDs of next generation as well as new
photoswitches and sensing devices.
2
80 nm
300nm
340 nm
380 nm
em = 450 nm
320 nm
3
4
60 nm
00 nm
em = 675 nm
400
450
500
550
600
650
700
750
3
00
350
400
450
500
Wavelength (nm)
Wavelength (nm)
Figure 8. (left) Excitation spectrum for solid complex 4 recorded at λem = 450 and 675 nm; (right) emission spectra of 4 recorded at different
excitations (λex = 280–400 nm).
Submitted to the European Journal of Inorganic Chemistry
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European Journal of Inorganic Chemistry
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A very similar dual luminescence has also been recognized for CP
II
6
demonstrating intraligand fluorescence and Mn -centered
phosphorescence bands at ~ 440-460 nm and 730 nm, respectively
Fig. 10a). Again, the ratio of these components strongly depends
(
upon the excitation wavelength. In contrast to 4, however, dual
emission of 6 persists up to 340 nm excitation, and upon further
increase in wavelength excitation, only blue band remains. This
behavior is in line with the excitation profile of the low-energy
emission band of 4 that demonstrates very weak intensity beginning
with ~ 370 nm (Fig. S13). By contrast, excitation curve recorded for
the high-energy emission band remains intensive up to ~ 420 nm
(Fig. S13). Owing to this feature, as well as longer wavelength
position of the phosphorescence band (730 nm, close to NIR
domain), luminescence chromaticity of 6 can be tuned in a wider
visible range: from a deep blue to a red (Fig. 10b). It should also be
remarked that phosphorescence lifetime of 6 being 21.5 µs is
4
6
2+
unusually short for the emitting T
ion,
τ
1
(G) → A
whereas the fluorescence lifetime is normal (τ
2
= 11.5 ns).
1
transition in Mn
[
1, 16-25]
1
= 1.2 ns,
Figure 9. CIE-1931 chromaticity diagram illustrating a change of the
emission color of solid 4 upon varying of excitation wavelength.
Figure 10. (left) Emission spectra of solid 6 recorded at different excitations (λex = 300–400 nm); (right) CIE-1931 chromaticity diagram illustrating a change
of the emission colour of 6 upon varying of excitation wavelength.
Emission spectrum of [Mn(L5)
3
][Mn(NCS)
4
]
(5) that
2
+
incorporates two potentially emitting Mn ions, is dominated by red
emission typical for octahedral Mn2+ ions (Fig. 11). The specific
green luminescence originated from d–d transitions in
2
–
[
Mn(NCS)
4
]
anion appears at ambient temperature as a weak
shoulder at 511 nm upon excitation with 300 nm light. The
suppression of the green emission of the tetrahedral Mn2 ions of 5
may be ascribed to effective Förster energy transfer from the
+
2
–
2+
[
Mn(NCS)
4
]
anion to [Mn(L5)
3
]
cation that further emits the
transferred energy. Previously, a similar phenomenon was earlier
proposed for the related “two-in-one” complexes, in which Mn2+
ions in T
Mn(L1)
d
and O
h
surroundings are simultaneously implemented, e.g.
4
[
25]
[
3
][MnBr ]. The red band of 5 has a mono-exponential
2
+
decay with the lifetime being peculiar for Mn -based
phosphorescence, i.e. τ = 1.11 ms.[16-25]
Figure 11. Emission spectra of solid 5 recorded at the different excitations
ex = 250–300 nm).
(λ
Conclusions
In summary, the reaction of Mn(NCS)
2
with diverse
bis(phosphine oxide) ligands, Ph
2
P(O)–X–(O)PPh
2
, has been
Submitted to the European Journal of Inorganic Chemistry
6
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201901213
II
systematically investigated and a series of molecular complexes and
CPs thus has been synthesized. The structure of the bis(phosphine
oxides) is demonstrated to play a decisive role in structure and
dimensionality of the products formed. For example, ligands with
2 2 2
[Mn (L1) (NCS) ]·2DMF (1·2DMF). To a solution of Mn(NCS) (16
mg, 0.09 mmol) in EtOH/acetone (2 mL), L1 (60 mg, 0.14 mmol) was
added. The mixture was stirred at ambient temperature for 1 h, and the
precipitated powder of 1 was then dissolved in DMF (1 mL). Resulting
solution was placed into a closed weighing bottle containing a diethyl
ether on a bottom. After keeping for 24 h, colorless crystals formed were
spacers X = “CH
2
”, “CH
2
CH
afford bis-chelating complexes of
Mn (O^O) ] kind. The reaction with the ligand bearing
2
C(=CH )C(=CH )” linker results in “two-in-one” complex
2 2 2 2 2
CH ” or “CH C(=CH )CH ”, upon
contact with Mn(NCS)
2
,
II
[
2
(NCS)
2
−1
collected and dried on air. Yield: 35 mg (67%). FT-IR (KBr, cm ): 388
“
2
(
(
(
(
(
(
m), 407 (w), 430 (m), 447 (w), 457 (w), 473 (w), 505 (vs), 519 (s), 569
m), 615 (w), 660 (m), 679 (s), 692 (vs), 721 (s), 743 (vs), 756 (s), 787
vs), 930 (w), 995 (m), 1028 (w), 1072 (m), 1092 (m), 1099 (m), 1123
s), 1180 (vs), 1202 (s), 1258 (w), 1317 (w), 1339 (w), 1360 (w), 1389
s), 1406 (w), 1439 (vs), 1483 (m), 1589 (m), 1661 (vs), 1973 (w), 2075
II
II
[
Mn (O^O)
octahedral Mn ions in a single structure. The acetylene-based
phosphine oxide, Ph P(O)C≡C(O)PPh , reacts with Mn(NCS) to
assemble 1D chain coordination polymer [Mn (O^O)
wherein octahedrally-coordinated metal ions are bridged by the
3 4
][Mn (NCS) ], incorporating both tetrahedral and
2
+
2
2
2
II
2
2 n
(NCS) ] ,
4 6 4 2
vs), 2085 (vs). Anal. Calcd for C58H58MnN O P S (1050.02): С, 60.6;
O^O
O^O
ligands in a [Mn( )Mn] fashion. Finally, Ph
2
P(O)CH
under similar conditions (r.t., air, EtOH/acetone media)
unexpectedly produces mixed-valent CP,
, in which MnII and Mn centers are
(NCS)
linked by the ligands into 1D chain. The photophysical study reveals
2 2 2
CH (O)PPh
Н, 5.1; N, 4.9; S, 5.6. Found: С, 60.3; Н, 4.9; N, 4.8; S, 5.5.
II
III
[
3 5 n 2
Mn Mn (L2) (NCS) ] (2). To a solution of Mn(NCS) (24 mg, 0.14
II
III
III
mmol) in EtOH/acetone (2 mL), L2 (60 mg, 0.14 mmol) was added. The
mixture was stirred at ambient temperature for 1 h, and a resulting
colorless solution was then filtered. A vial with the filtrate then was
placed into a closed weighing bottle containing a diethyl ether on a
bottom. After keeping for 24 h, colorless crystals formed were collected
and dried on air. Yield: 55 mg (47%). FT-IR (KBr, cm ): 420 (w), 478
(m), 500 (m), 511 (s), 534 (vs), 554 (s), 677 (m), 692 (s), 727 (vs), 750
(s), 762 (m), 997 (w), 1026 (w), 1070 (m), 1099 (s), 1123 (s), 1140 (m),
1163 (vs), 1180 (s), 1287 (w), 1314 (w), 1337 (w), 1369 (w), 1389 (w),
1408 (m), 1437 (s), 1483 (w), 1589 (w), 1655 (m), 1692 (w), 2039 (s),
[
Mn Mn (O^O)
3
5 n
]
II
a noticeable dual luminescence for [Mn (O^O)
2
(NCS)
Ph (O)PPh
2
(O)PPh ligands. In the solid-state at room
2
] complexes
basing
Ph P(O)CH
on
C(=CH
2
P(O)CH
2
CH
2
CH
2
2
and
2
2
2
)CH
2
−
1
temperature both complexes manifest multicolor emission displayed
by blue and red complementing bands, which are originated from
2
+
intraligand fluorescence and Mn -centered phosphorescence,
respectively. The relative ratio of these bands is effectively
controlled by excitation wavelength that provides a powerful tool for
fine-tuning the luminescence color from a deep-blue to a red. In
general, the synthesized compounds, to our knowledge, are
essentially first emissive MnII thiocyanate complexes. On a
fundamental level, the findings presented contribute to coordination
chemistry and photophysics of manganese compounds. From a
practical viewpoint, the new results open up rich opportunities for
design of stable and low-cost single molecule-based materials with
tunable emission characteristics.
2
(
045 (s), 2068 (vs), 2085 (s). Anal. Calcd for C83
1691.53): С, 58.9; Н, 4.3; N, 4.1; S, 9.5. Found: С, 59.1; Н, 4.3; N, 4.0;
S, 9.2.
2 5 6 6 5
H72Mn N O P S
II
[
2 2 2
Mn (L3) (NCS) ] (3). To a solution of Mn(NCS) (16 mg, 0.09 mmol)
in EtOH/acetone (2 mL), L3 (64 mg, 0.14 mmol) was added. The
mixture was stirred at ambient temperature for 1 h, and the precipitated
white powder of 3 was centrifuged and dried in vacuum. Yield: 30 mg
63%). FT-IR (KBr, cm ): 397 (w), 426 (w), 447 (w), 505 (s), 538 (s),
55 (s), 664 (m), 694 (vs), 723 (vs), 746 (s), 822 (w), 934 (w), 943 (w),
997 (w), 1028 (w), 1070 (w), 1103 (s), 1123 (s), 1171 (vs), 1329 (w),
−
1
(
5
Experimental Section
1
2
4
341 (w), 1350 (w), 1398 (m), 1437 (s), 1485 (w), 1591 (m), 2064 (vs),
085 (vs). Anal. Calcd for C56 (1059.98): С, 63.4; Н,
2 4 4 2
H52MnN O P S
Materials and Methods: The reactions were carried out under
.9; N, 2.6; S, 6.1. Found: С, 63.1; Н, 4.7; N, 2.9; S, 6.5.
2 2
ambient conditions (23–25 °C, air). MnCl ·4H O (≥99.0%, Aldrich),
II
[
Mn (L4)
2
(NCS)
2
] (4). To a solution of Mn(NCS)
2
(12 mg, 0.07 mmol)
NaNCS (99.9%, Reactiv) and MeCN (HPLC grade, Cryochrom) were
used as purchased. The ligands L1–4[54] and L5[55] were prepared
following the published procedures. L6 was synthesized by oxidation of
in EtOH/acetone (2 mL), L4 (60 mg, 0.13 mmol) was added. The
mixture was stirred at ambient temperature for 1 h, and the precipitated
white powder of 4 was centrifuged and dried in vacuum. Yield: 25 mg
the corresponding bis-phosphine (98%, Aldrich) in H
system.
2 2 2
O /H O/acetone
−
1
(
66%). FT-IR (KBr, cm ): 409 (w), 432 (m), 463 (m), 469 (m), 503 (s),
5
8
13 (vs), 544 (s), 588 (vs), 692 (vs), 719 (vs), 748 (s), 777 (m), 789 (w),
33 (s), 858 (w), 868 (w), 920 (m), 995 (w), 1028 (w), 1074 (m), 1103
PXRD patterns were recorded on
a Shimadzu XRD-7000
diffractometer (Cu-Kα radiation, Ni – filter, 3–35° 2θ range, 0.03° 2θ
step, 5s per point). FT-IR spectra were measured on a Bruker Vertex 80
spectrometer at ambient temperature. Thermogravimetric analyses
(s), 1123 (s), 1150 (s), 1179 (vs), 1231 (m), 1240 (m), 1283 (m), 1312
(w), 1321 (w), 1341 (w), 1383 (m), 1395 (m), 1439 (s), 1487 (w), 1593
(m), 1636 (m), 1703 (vw), 1815 (vw), 1834 (vw), 1892 (vw), 1910 (vw),
(
2 3
TGA/DTG/c-DTA) were conducted in a closed Al O pan under argon
flow at 10 °C/min–1 heating rate using a NETZSCH STA 449 F1 Jupiter
58 52 2 4 4 2
2079 (vs). Anal. Calcd for C H MnN O P S (1083.95): С, 64.3; Н,
4
.8; N, 2.6; S, 5.9. Found: С, 64.0; Н, 4.6; N, 2.6; S, 5.6.
STA instrument.
II
II
[
3 4 2
Mn (L5) ][Mn (NCS) ] (5). To a solution of Mn(NCS) (16 mg, 0.09
Photophysical measurements: Photoluminescence and excitation
luminescence spectra were recorded at room temperature using
Fluorolog-3 (Horiba Jobin Yvon) equipped with a 450 W ozone-free Xe
lamp, double grating excitation and emission monochromators.
Emission and excitation spectra were corrected for source intensity
mmol) in EtOH/acetone (2 mL), L5 (60 mg, 0.13 mmol) was added. The
mixture was stirred at ambient temperature for 1 h, and the precipitated
powder of 5 was centrifuged and dried in vacuum. Yield: 90 mg (58%).
−
1
FT-IR (KBr, cm ): 428 (w), 465 (w), 480 (w), 505 (s), 538 (vs), 577 (s),
5
9
96 (s), 615 (w), 673 (m), 696 (vs), 729 (vs), 754 (s), 775 (m), 914 (w),
66 (m), 997 (w), 1026 (w), 1072 (m), 1101 (s), 1121 (s), 1179 (vs),
(
lamp and grating) and emission spectral response (detector and grating)
by standard correction curves. The luminescence decays (Figures S8–10)
were recorded on the same instrument.
1207 (s), 1314 (w), 1383 (w), 1416 (m), 1437 (s), 1483 (m), 1589 (w),
2 4 6 6 4
1630 (w), 1722 (w), 2054 (vs). Anal. Calcd for C88H72Mn N O P S
Mn(SCN)
2
. To a solution of MnCl
2
·4H
2
O in EtOH, solution of NaSCN
in acetone was added and the mixture was stirred at ambient temperature
for 10 min. The precipitated NaCl was filtered-off and the freshly
(1705.43): С, 62.0; Н, 4.2; N, 3.3; S, 7.5. Found: С, 62.1; Н, 4.4; N, 3.3;
S, 7.6.
II
[
Mn (L6)
2
(NCS)
2
]
n
(6). To a solution of Mn(NCS)
2
(16 mg, 0.09
2
prepared Mn(SCN) was then used for synthesis of 1–6.
mmol) in EtOH/acetone (2 mL), L6 (40 mg, 0.09 mmol) was added. The
Submitted to the European Journal of Inorganic Chemistry
7
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201901213
[
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cm ): 432 (w), 482 (w), 515 (s), 534 (vs), 584 (w), 619 (vw), 689 (s),
06 (m), 729 (s), 750 (m), 816 (vs), 997 (m), 1026 (w), 1070 (w), 1101
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Submitted to the European Journal of Inorganic Chemistry
8
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European Journal of Inorganic Chemistry
10.1002/ejic.201901213
FULL PAPER
First representatives of luminescent
MnII thiocyanate complexes were
Dual luminescence
Maria P. Davydova, Irina A. Bauer,
Valery K. Brel, Mariana I. Rakhmanova,
Irina Yu. Bagryanskaya, and Alexander
V. Artem’ev*
assembled reacting the Mn(NCS)
diverse bis(phosphine oxides) ligands
of Ph P(O)–X–(O)PPh type. Some of
2
with
2
2
such complexes feature an intriguing
solid-state dual emission expressed by
Manganese(II) thiocyanate complexes
with bis(phosphine oxide) ligands:
synthesis and excitation wavelength-
dependent multicolor luminescence
“
blue” and “red” bands which are
originated
fluorescence
from
and
intraligand
Mn -centered
2
+
phosphorescence, respectively.
Submitted to the European Journal of Inorganic Chemistry
9
This article is protected by copyright. All rights reserved.