Synthesis and characterization of unique new lithium, sodium and potassium coordination polymers

Article abstract of DOI:10.1016/j.ica.2018.04.045

Five new alkali metal coordination compounds [Li(NPG)](1a), [Na(NPG)₂]?2H₂O(2a), [C₈H₅KO₄](3a), [Li(NPA)₂H₂O](1b) and [Na(NPA)₂](2b) wherein (NPG = N-phthaloyl glycine, NPA = N-phthaloyl-?-alanine) have been synthesized and characterized by means of X ray single crystal analysis, Infrared spectroscopy (IR), Thermogravimetric analysis (TGA) and Florescence spectroscopy. The compounds 1a, 2a, 3a and 2b showed metal directed self-assembly supramolecular network structures. The crystal structure of compounds 1a and 1b showed distorted tetrahedral geometry with coordination number 4 around lithium. The carboxylate coordination modes were η²μ³and η¹μ¹ in 1a and 1b respectively. The compounds 2a and 2b exhibited distorted octahedral geometry with coordination number 6 around sodium. The carboxylate coordination mode in 2a and 2b is η²μ². The objective was to synthesize potassium complex [K(NPG)], but N-phthaloyl glycine was hydrolysed due to exothermic reaction in the presence of strong base, resulted, the formation of 3a. The multiple coordination modes of alkali metal ions to the carboxylate and ring carbonyl oxygen atoms of NPG and NPA produced unique three dimensional architectures. The compounds 1b and 2b showed two strong fluorescence emissions enhancement (blue emission maxima) with greater intensity comparative to NPA, while the compounds 1a and 2a showed two weak fluorescence emissions with less intensity comparative to ligand (NPG). The base hydrolysis of NPG with in the compound 3a resulted the change of ligand based fluorochrome, which produced different shape emission spectrum as compared to other compounds.

Full text of DOI:10.1016/j.ica.2018.04.045

Accepted Manuscript
Synthesis and characterization of unique new lithium, sodium and potassium
coordination polymers
Muhammad Nadeem, Moazzam H. Bhatti, Uzma Yunus, Mazhar Mehmood,
Hafiz Muhammad Asif, Shoaib Mehboob, Ulrich Flörke
PII:
S0020-1693(18)30231-7
https://doi.org/10.1016/j.ica.2018.04.045
ICA 18236
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
10 February 2018
18 April 2018
22 April 2018
Please cite this article as: M. Nadeem, M.H. Bhatti, U. Yunus, M. Mehmood, H.M. Asif, S. Mehboob, U. Flörke,
Synthesis and characterization of unique new lithium, sodium and potassium coordination polymers, Inorganica
Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.04.045
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Synthesis and characterization of unique new lithium, sodium and potassium coordination
polymers
Muhammad Nadeema,b, Moazzam H. Bhattia*, Uzma Yunusa , Mazhar Mehmoodb, Hafiz Muhammad Asifc, Shoaib
Mehboobb, Ulrich Flörked
a Department of Chemistry, Allama Iqbal Open University, Islamabad, Pakistan
b
National Center for Nanotechnology, Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering and
Applied Sciences (PIEAS), Nilore 45650, Islamabad, Pakistan
cDepartment of Chemistry, Khwaja Fareed University of Engineering and Information Technology (KFUEIT), Rahim Yar Khan, Pakistan
dAnorganische und Analytische Chemie, Fakultät für Naturwissenschaften,Universität Paderborn, Warburgerstrasse 100, D-33098
Paderborn, Germany
Abstract
Five new alkali metal coordination compounds [Li(NPG)](1a), [Na(NPG)2]2H2O(2a),
[C8H5KO4](3a), [Li(NPA)2H2O](1b) and [Na(NPA)2](2b) wherein (NPG=N-phthaloyl glycine,
NPA= N-phthaloyl-ß-alanine) have been synthesized and characterized by means of X ray single
crystal analysis, Infrared spectroscopy (IR), Thermogravimetric analysis (TGA) and Florescence
spectroscopy. The compounds 1a, 2a, 3a and 2b showed metal directed self-assembly
supramolecular network structures. The crystal structure of compounds 1a and 1b showed
distorted tetrahedral geometry with coordination number 4 around lithium. The carboxylate
coordination modes were η2µ3and η1µ1 in 1a and 1b respectively. The compounds 2a and 2b
exhibited distorted octahedral geometry with coordination number 6 around sodium. The
carboxylate coordination mode in 2a and 2b is η2µ2. The objective was to synthesize potassium
complex [K(NPG)], but N-phthaloyl glycine was hydrolysed due to exothermic reaction in the
presence of strong base, resulted, the formation of 3a. The multiple coordination modes of alkali
metal ions to the carboxylate and ring carbonyl oxygen atoms of NPG and NPA produced unique
three dimensional architectures. The compounds 1b and 2b showed two strong fluorescence
emissions enhancement (blue emission maxima) with greater intensity comparative to NPA,
while the compounds 1a and 2a showed two weak fluorescence emissions with less intensity
comparative to ligand (NPG). The base hydrolysis of NPG with in the compound 3a resulted the

change of ligand based fluorochrome, which produced different shape emission spectrum as
compared to other compounds.
Keywords: N-phthaloyl glycine; N-phthaloyl-ß-alanine; coordination polymer; X-ray;
fluorescence spectroscopy.
1. Introduction
The most part of co-ordination chemistry is concerned with transition metal ions;
however, S-block metal ions have attained generally little consideration. [1] Alkali or
alkaline earth metal cations being non-dangerous and soluble in aqueous media are used
in preference to coordinate with transition [2] or lanthanide [3] metal ions. The alkali and
alkaline earth metal complexes are used in pharmaceuticals, [4] dyes, [5] and pigments
[6]. The S-block cations have prime significance in solid-state structure and behave like a
bridge in the intermolecular interactions. [7, 8] Alkali metal ions containing coordination
polymeric structures are regularly less examined in detail. [9] In any case, this is a serious
issue which is worth researching by keeping in mind the end goal to better comprehend
the properties of these solid-state compounds. As linkers, carboxylates offer a variety of
possible metal-binding motifs allowing for the formation of wide arrays of extended
structures. [10-12] The development of various dimensional coordination polymer
systems containing alkali or alkaline earth metal ions are predominantly taking into
account due to anionic oxygen contributor. [13] The combination of alkali metal
coordination polymers can be accomplished utilizing a salt and forming low-dimensional
structures with neutral donor ligands, the later going about as synthetic scissors on the
underlying material. [13] The basic differences of coordination polymers fundamentally
influenced by the decision of the ligands, [14-16] metal ligand proportions, [17, 18]

solvents, [19-22] and counterions. [23] These variations produce wide range of self-
assembled structures. [19-23] Mixed alkali and transition metal coordination polymer
with 2, 6-Pyridinedicarboxylate produced robust structure with enhanced chemical and
physical properties. [24, 25] The presence of two carbonyl groups with central nitrogen
atom in Phthalimide derivatives [26] make them alluring to design supramolecular
networks that find critical applications in catalytic reactions [27] and have been employed
for the synthesis of chiral esters. [28] They have also used as biological probe as their
fluorescence properties are highly environment sensitive. [29] The Phthalimide group acts
as a protecting group for amines and amino acids. [30, 31] The N-protected amino acids
are used for the synthesis of peptide bonds in the solid phase synthesis. [32]
Co-ordination chemistry of N-protected amino acids with metal ions is used to understand
the coordination chemistry of proteins. [33] Many kinds of proteins within the body need
metal ions to work, which can also be activated or deactivated by metal ions. These
reversible reactions are caused by ligation of the metal ions and the proteins. If one has an
understanding of the basic metal ion, N-protected α-amino acid complexation, then one
could better identify the coordination site within the proteins. N-phthaloyl glycine has a
variety of applications in medicinal chemistry, pharmaceuticals as dietary supplements,
analytical and is used as antimicrobial reagents. [34]
In the present investigation we report the synthesis and luminescence properties of
selected alkali metal compounds with NPG and NPA as ligands.

SCHEME OF WORK
When n=1, N-phthaloyl glycine
n=2, N-Phthaloyl-Beta-Alanine
(a)
(b)
(c)
(d)
Scheme 1. Schematic illustration of the synthetic route for ligands (a) and complexes (1a and 2a) (b), 3a (c),
and (1b and 2b) (d).
2. Experimental details
2.1. Reagents and Chemicals
NPG and NPA were prepared by the reported methods. [35] The synthesis scheme of ligands
and complexes are presented in scheme 1. All solvents used for the synthesis were freshly
distilled prior to use.

2.2. Instruments and Measurements
Nicolet iS 10 FTIR spectrophotometer was used to produce infrared spectra for all compounds in
the range 4000-400 cm-1 through KBr discs. Melting points were determined via Gallen Kamp
electro thermal apparatus, Cat No.MPD350, Sanyo, UK. Fluorescent emission spectra were
recorded on F-7000 FL spectrophotometer 2133-007. Thermal decomposition patterns (TG and
DTA) of all compounds were carried out under nitrogen atmosphere up to 800°C utilizing a
heating rate of 10°C/min on a DTG-60H Simultaneous DTA-TG Analyzer. Raman spectroscopy
was carried out using high resolution Raman spectroscopy system model MST 4000A
(Germany). In Raman spectrometer main elements of setup are, laser sources 532 nm and 442
nm, samples slides and chamber light collection optics detection system.
2.3. Synthesis of 1a and 2a
An aqueous solution of metal (Li/Na) hydroxide (9.7mmol in 50ml) was added drop wise
to well-stirred solutions of NPG (9.7mmol) in ethanol (40 ml) at room temperature
separately. The pH of solution was adjusted to 6-7 and then stirred with heating (60 ºC)
for next 3 hours, after that set aside for crystallization. After four weeks, 0.90g (43%
yield) for 1a and 0.85g (18% yield) for 2a of colourless single crystals of good quality
were obtained.
2.4. Synthesis of 3a
An aqueous solution of potassium hydroxide (9.8mmol in 50ml) was added drop wise to a
well-stirred solution of NPG (9.8mmol) in ethanol (40 ml) at room temperature. The
solution was stirred for next 4 hours with heating. Due to intense heat the base hydrolysis
of NPG had occurred [36] and phthalic acid is formed as an intermediate product. This
phthalic acid reacted with KOH to form colourless crystals of potassium phthalate
confirmed by single X-rays crystal analysis.

2.5. Synthesis of 1b and 2b
An aqueous solution of metal (Li/Na) carbonate (4.5mmol in 50ml) was added drop wise
to a well-stirred solution of NPA (9.1mmol) in ethanol (40 ml) at room temperature
separately. The pH (6-7) adjusted solution was stirred with heating (60 ºC) for next 4
hours and then set aside for crystallization. After four weeks, 0.48g (48% yield) for each
1b and 2b of colourless single crystals were obtained.
3.
Results and Discussion
The physical characteristics of the synthesized compounds are given in Table 1.
Table 1. Physical properties data of the compounds 1a, 2a, 3a, 1b and 2b.
Compounds
Formula
M.P (oC)
%Yield
320
298
43
18
1a
2a
C10 H6 N O4 Li
C20 H17 N2 O10 Na
<340
300
20
48
48
3a
1b
2b
C8 H5 O4 K
C22 H19 N2 O9 Li
C22 H17 N2 O8 Na
258
3.1. Infrared and Raman spectra
FTIR spectra of all compounds were registered in the KBr matrix presented in Fig. 1(a)
and Table 2. The Raman spectra were taken in the range of 2000-150 cm-1 showed in Fig.
1(b). The very broad band at 3568 cm-1 appeared due to stretching frequency ν(OH) of
acid appeared in the spectrum of free N-phthaloyl glycine disappeared in the spectra of its
compounds 1a and 2a confirmed that, the hydrogen ion of carboxylate group of free N-
phthaloyl glycine was substituted by the metal ions by de-protonation. [33] IR spectrum
of 1a and 2b showed in Fig. 1 devoid of any absorption beyond 3310 cm-1, which clearly
indicates the absence of any sort of water molecule [1] in the compounds 1a and 2b, the
sharp absorption observed at 3476 cm-1 in the compound 2a indicates the presence of
lattice water molecule, medium broad absorption observed for 1b at 3413 cm-1 proves the

presence of coordinated water molecule. [37-39] The bands at 3128 (O-H stretch) and
1718 cm-1 (C=O) for 1b indicate that one of the carboxylate groups remains protonated.
The O-H stretch for 3a is present at 3127 cm-1 confirmed the presence of protonated
carboxyl group. The ring carbonyl single band of N-phthaloyl moiety for ligands (NPG
&NPA) and compounds 1a, 2a, 1b and 2b appeared in the range 1779-1770 cm-1 (IRKBr),
1755-1779 (Raman), while absent for 3a. This confirms the hydrolysis of NPG in 3a. The
Raman spectra peaks at 1715 cm-1 for 2a, 1703 cm-1 for 1b and 2b attributed to the
stretching vibration of carboxyl group (C=O) while absent for 1a and 3a. [39] The
corresponding stretching vibration for IR are 1732 cm-1 for NPG, 1731 cm-1 for 1a, 1720
cm-1 for 2a, 1717 cm-1 for 3a, two peaks at 1722 cm-1 and 1705 cm-1 for NPA, 1718 cm-1
for 1b, 1716 cm-1 for 2b. The characteristic asymmetric (ma) and symmetric (ms)
stretches due to the carboxylate group (COO-1) are as follows. [39]
1628 cm-1 and 1401 cm-1 (IRKBR), absent in Raman for 1a
1465 cm-1 and 1319 cm-1(IRKBR), 1600 cm-1 and 1409 cm-1 (Raman) for 2a
1559 cm-1 and 1399 cm-1, (IRKBR), 1588 cm-1 and 1484 cm-1 (Raman) for 3a
1617 cm-1 and 1400cm-1, (IRKBR), 1600 cm-1 and 1182 cm-1 (Raman) for 1b
1608 cm-1 and 1321 cm-1, 1600 cm-1 and 1179 cm-1 (Raman) for 2b.
Table 2. Infrared (cm-1) spectral data of compounds 1a, 2a, 3a, 1b and 2b.
Compounds
ν(OH) ν(OH)
ν(OH)
ν(C=O)
ν(C=O)
νas(COO-)
νsy(COO-) ν(C-OH) δ(C-OH) ν(M-O)
carbox lattice
coordinated carboxylic carbonyl
water
ylic
water
NPG
1a
3568
-
-
-
-
1732
1731
1720
1717
1770
1779
1775
-
-
-
1217
-
994
-
-
-
1628
1465
1559
-
1401
1319
1399
-
567, 582
534, 599
442
2a
-
3476
-
-
-
3a
3127
3206
3128
-
-
-
-
-
1264
1212
1230
1078
1001
1010
NPA
1b
-
1722, 1705 1770
-
3413
1718
1772
1617
1400
531
2b
-
-
1716
1770
1608
1321
-
-
532
ν = stretching,δ= bending, as = asymmetrical, sy=symmetrical

(a)
(b)
Fig. 1. FTIR spectra (a) and Raman spectra (b) of compounds 1a, 2a, 3a, 1b and 2b.
3.2. Crystal Structure Description of compounds
3.2.1. Structure Determination
The intensity data for all compounds were recorded using a Bruker SMART CCD area-
detector diffractometer with graphite monochromatic MoKα radiation (λ = 0.71073 Å) at
T = 130(2) K. Semi-empirical absorption correction applied from equivalent reflections
.
Structure solutions were obtained by direct methods [40] and refined through full-matrix
least squares refinements [40] based on F2. All atoms expect hydrogen were refined an-
isotropically, H-atoms were clearly located from difference fourier maps, refined at
idealized positions riding on the parent atoms with isotropic displacement parameters
Uiso(H) = 1.2Ueq(C/O) and C-H 0.95-0.98 Å. Specific crystal data and structure
refinement details are given in Table 3, selected bond lengths as well as selected bond
angles are given in Table 4 and 5 respectively.
3.2.2. Specific structural details of 1a
Single crystal X-ray diffraction analysis, revealed the formation of the lithium compound
[C10H6NO4Li] (1a). Each lithium atom (Fig. 2a) is coordinated by three carboxylate

oxygen atoms [O(3), O(3B), O(4B)] in a bridging mode and one carbonyl oxygen atom
[O(1A)]. The selected bond angles(deg): O(3)-Li(1)-O(4)#1, 109.57º(14); O(3)-Li(1)-
O(3)#2, 113.88º(14); O(4)#1-Li(1)-O(3)#2, 111.96º(16); O(3)-Li(1)O(1)#3, 103.92º(15);
O(4)#1-Li(1)-O(1)#3, 110.66º(14); O(3)#2-Li(1)-O(1)#3, 106.51º(14) suggested the
formation of slightly distorted tetrahedral geometry of Lithium compound with
coordination number 4. The two carbonyl groups present in NPG behaved differently, one
group with bond length 1.209(2) Å coordinated with metal while other (1.207(2)) remains
uncoordinated. The carboxylate bond lengths are 1.256(2) Å & 1.239(2) Å for O(3)-
C(10), O(4)-C(10) respectively with coordination mode η2µ3.[41] The bond length
between lithium and oxygen is different for different motifs. The bond lengths [Li(1)-
O(3) 1.909(3) Å], [Li(1)-O(4A) 1.909(3) Å], [Li(1)-O(3B) 1.918(3) Å], [Li(1)-O(1A)
1.936(3)Å] indicate that the carbonyl oxygen atom makes weaker bond with lithium as
compared to the carboxylate oxygen atoms. Further the compound 1a crystallized in the non-
centrosymmetric space group P 2(1); however, the absolute configuration cannot be determined
due to the absence of anomalous scattering effects. The schematic diagram of the
coordination behaviour of lithium in compound 1a is shown in Fig. 2b. The lithium metal
directed self-assembly (Fig. 2c) produced unique supramolecular structure.

Fig. 2. (a) View of the molecular structure of LiNPG (1a) showing the coordination geometry about Lithium,
anisotropic displacement ellipsoids are drawn at the 50% probability level (colour codes: Li, pink; C, grey; O, red;
N, blue; H, green), symmetry transformations used to generate equivalent atoms for 1a: #1, x, y-1, z; #2, -x+1, y-1/2,
-z+1; #3, -x+2, y-1/2, -z+1; #4, -x+1, y+1/2, -z+1; #5, -x+2, y+1/2, -z+1; #6, x, y+1, z. (b) Schematic diagram of the
coordination behaviour of lithium in compound 1a. (c) Self-assembly diagram along a axis of 1a.
3.2.3. Specific structural details of 2a
Single-crystal X-ray diffraction analysis, showed the formation of the sodium compound
[C20H13N2O8Na].2H2O (2a). Each sodium atom is coordinated by four carboxylate
oxygen atoms [O(3), O(3C), O(4D), O(4E)] in a bridging mode and two carbonyl oxygen
atoms [O(1A), O(1B)] presented in Fig. 3a. The measured bond distance for O3-C10 is
1.227(2) Å and for O4-C10 is 1.291(2) Å in single crystallographically independent ligand NPG,
the difference is significant and might indicate that O4 is hemiprotonated. This supposition is
also supported by the fact that the compound was crystallized in acidic environment (pH 6-7).
Indeed it was not possible to derive meaningful and eventual O-H positions from the difference
maps. The selected bond angles (deg) suggested the formation of distorted octahedral

geometry with coordination number 6. The two carbonyl groups showed the similar
behaviour as in 1a, but here the difference of C-O bond length for metal coordinated
(1.212(2) Å) and uncoordinated (1.206(2) Å) is much more evident than 1a. The
carboxylate coordination mode is η2µ2 bridging. Two solvent water molecules are present
per formula unit. The schematic diagram of the coordination behaviour of sodium in
compound 2a and supramolecular structure is shown in Fig. 3b and 3c.
Fig. 3. (a) View of the coordination environment of Na for NaNPG (2a), anisotropic displacement
ellipsoids are drawn at the 50% probability level (colour codes: Na, blue; C, grey; O, red; N, blue; H, green),
symmetry transformations used to generate equivalent atoms for 2a: #1, -x, -y+1, -z+2; #2, x, y-1, z; #3, -x, -y, -z+2;
#4, x, -y, z-1/2; #5, -x, y, -z+5/2; #6, x, y+1, z. (b) schematic diagram of the coordination behaviour of sodium
in compound 2a. (c) Self-assembly diagram along c* axis of 2a.
3.2.4. Specific structural details of 3a
Single crystal X-ray diffraction analysis, confirmed the formation of the potassium
compound [C8H5O4K] (3a) (Fig. 4a). The co-ordination number of K is 7 with pentagonal
bipyramidal (Fig. 4b). The self-assembly is evident in Fig. 4c.

Fig. 4. (a) View of the molecular structure of 3a showing the coordination geometry about potassium, anisotropic
displacement ellipsoids are drawn at the 50% probability level, (colour codes: K, blue; C, grey; O, red; H, green),
symmetry transformations used to generate equivalent atoms for 3a: #1, -x+1/2, y, z-1/2; #2, -x, -y, z-1/2; #3, -x, -y,
z+1/2; #4, -x+1/2, y, z+1/2. (b) Schematic diagram of the coordination behaviour of sodium in compound 3a. (c)
Self-assembly of 3a along b* axis.
3.2.5. Specific structural details of 1b and 2b
The single crystal X-ray diffraction displayed the formation of lithium compound
[C22H17N2O8Li.H2O] (1b) and [C22H17N2O8Na] (2b). The structural details of 1b is
described as, each lithium atom is coordinated by four oxygen atoms labelled as O(4),
O(5), O(8) and O(9) which are related to the three NPA ligands and one water molecule
shown in Fig. 5(a) along with schematic view in Fig. 5 (b). The carboxy oxygen atoms
O(4) and O(8) are related to two different crystallographically independent NPA ligands. One
NPA ligand which is coordinated to Li(I) ion through O(4) has been refined in protonated form,

the bond length difference between C11-O3 (1.310(2) Å) and C11-O4 (1.211(2) Å) is evident,
suggesting the protonation of O(3) as O(3)-H(3)). The second carboxy group oxygen O(8)
coordinated to Li (I) ion is related to the other crystallagraphic independent deprotonated NPA
ligand, bond distances C22-O7 and C22-O8 of the deprotonated carboxy group are nicely the
same. The ring carbonyl O(5) atom related to deprotonated NPA ligand also connected to Li(I)
ion through the third coordination bond around lithium. The bond length is mentioned here for
two ring carbonyl of deprotonated NPA, one is coordinated C12-O5 (1.216Å) and other is
uncoordinated C19-O6 (1.210(2) Å). One coordinated water molecule having O(9) atom refined
as neutral ligand forming forth coordination bond with Li(I) ion. The selected bond angles
(deg) suggest the formation of distorted tetrahedral geometry with coordination number 4
around lithium. The carboxylate coordination mode is η1µ1. For 2b one crystallographically
independent NPA ligand is refined, but from molecular formula the metal to ligand ratio
found is 1:2, also there is reasonable difference in the bond distance of C11-O3 (1.226 Å)
and C11-O4 (1.291Å) relating to carboxy group of refined NPA, the third important fact is
that 2b was crystallized in acidic pH (6-7) environment. All aforementioned facts support the
claim that ligand NPA is not fully deprotonated but it is hemiprotonated. The crystallographic
limits can be understood as previously discussed in the crystallographic discussion part of
compound 2a. Each sodium atom in 2b is coordinated by four carboxylate oxygen atoms
[O(3B), O(3C), O(4B), O(4C)] in a bridging mode and two ring carbonyl oxygen atom
[O(1), O(1A)] (see Fig. 5c) producing self-assembly structure shown in Fig. 6e. The
selected bond angles (deg) suggest the formation of distorted octahedral geometry with
coordination number 6. The two carbonyl groups present in n-phthaloyl ß-alanine behave

differently as O(1) coordinates to Na while O(2) remains uncoordinated. The carboxylate
coordination mode is η2µ2 bridging. The schematic diagram of 2b is present in Fig. 5d.
Fig. 5. The coordination environment of Li(I) ion for compound 1b (a) and Na(I) ion for compound 2b (c),
anisotropic displacement ellipsoids are drawn at the 50% probability level, (colour codes: Li, pink; C, grey; O, red;
N, blue; H, green for 1b and Na, blue; C, grey; O, red; N, blue; H, green for 2b), symmetry transformations used to
generate equivalent atoms: #1, -x+2, -y+1, -z+1 for 1b and #1, x, y-1, z; #2, -x+2, -y+2, -z; #3, x-1, y-1, z; #4, -x+3,
-y+2, -z; #5, -x+2, -y+1, -z; #6, x+1, y+1, z; #7, x, y+1, z for 2b. (b) and (d) Schematic diagram of the coordination
behavior of lithium and sodium respectively. (e) Self-assembly of 2b along b axis using ball and stick model.

Table 3. Crystal data and structure refinement details of compounds for 1a, 2a, 3a, 1b and 2b.
1a
2a
3a
1b
2b
Empirical formula
C10 H6 Li N O4
C20 H17 N2 Na O10
C8 H5 K O4
C22 H19 Li N2 O9
C22 H17 N2 Na O8
Formula weight
T (K)
211.1
130(2)
467.34
130(2)
204.22
130(2)
462.33
130(2)
459.36
130(2)
Wavelength (Å)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
0.71073
Monoclinic
P2(1)
7.2750(19)
4.8795(13)
13.416(4)
90
98.259(5)
90
471.3(2)
2
1.488
0.115
216
0.48 x 0.22 x 0.19
1.53 to 27.88
4497
1257
0.0176
99.90%
0.71073
Orthorhombic
Pbcn
33.517(3)
5.0923(5)
11.9039(11)
90
90
90
2031.7(3)
4
1.528
0.142
968
0.48 x 0.33 x 0.25
2.43 to 27.88
17568
2419
0.0244
0.999
0.71073
Orthorhombic
Pca2(1)
9.5684(9)
13.2423(12)
6.4190(6)
90
0.71073
Triclinic
P-1
0.71073
Monoclinic
P2(1)/n
5.2397(4)
7.0386(6)
27.744(2)
90
91.792(2)
90
1022.68(14)
2
1.492
0.133
476
0.48 x 0.20 x 0.12
1.47 to 27.86
9219
2441
0.0222
6.9625(6)
10.3480(9)
15.8169(13)
102.721(2)
98.527(2)
100.575(2)
1071.36(16)
2
1.433
0.112
480
0.47 x 0.21 x 0.11
2.07 to 27.88
10271
5081
0.0212
α (°)
β (°)
γ (°)
90
90
Volume (Å3)
Z
813.34(13)
4
1.668
0.627
416
0.38 x 0.20 x 0.10
1.54 to 27.87
6954
1921
0.0208
0.998
D calc (Mg/m3)
Absorption coefficient(mm-1)
F(000)
Crystal size (mm3)
θ(°) range
Reflections collected
Independent reflections
R(int)
Completeness to θ = 27.88°
99.60%
100.00%
Max. and min. transmission
CCDC Number
0.9785 and 0.9469
870359
0.9654 and 0.9351
870722
0.9399 and 0.7966
872685
0.9878 and 0.9493
873800
0.9843 and 0.9391
876492
Table 4. Selected metal-oxygen bond distances (Å) for 1a, 2a, 3a, 1b and 2b.
1a (M-O)&
(M-M)
Bond
Distance(Å)
2a (M-O)
Bond
Distance(Å)
3a (M-O)
Bond
Distance(Å)
1b(M-O)
Bond
Distance(Å)
2b (M-O)
Bond
Distance(Å)
Li(1)-O(3)
1.909(3)
1.909(3)
1.918(3)
1.936(3)
3.032(3)
3.032(3)
1.936(3)
1.918(3)
Na(1)-O(4)#1
Na(1)-O(4)#2
Na(1)-O(3)#3
Na(1)-O(3)
2.2946(9)
2.2946(9)
2.3797(9)
2.3797(10)
2.4130(10)
2.4130(10)
2.4130(10)
2.2946(9)
K(1)-O(4)#1
K(1)-O(4)
2.6271(11)
2.7441(13)
2.7724(11)
2.7875(11)
2.8501(11)
2.9648(11)
3.1076(12)
3.1076(12)
Li(1)-O(8)#1
Li(1)-O(9)
Li(1)-O(4)
Li(1)-O(5)
O(8)-Li(1)#1
------------
1.900(3)
1.903(3)
1.938(2)
1.960(2)
1.900(3)
------------
------------
------------
Na(1)-O(4)#1
Na(1)-O(4)#2
Na(1)-O(3)#3
Na(1)-O(3)#4
Na(1)-O(1)
2.3065(11)
2.3065(11)
2.3668(11)
2.3668(11)
2.4347(11)
2.4347(11)
2.3065(11)
2.3668(11)
Li(1)-O(4)#1
Li(1)-O(3)#2
Li(1)-O(1)#3
Li(1)-Li(1)#2
Li(1)-Li(1)#4
O(1)-Li(1)#5
O(3)-Li(1)#4
K(1)-O(3)
K(1)-O(3)#2
K(1)-O(2)
Na(1)-O(1)#4
Na(1)-O(1)#5
O(1)-Na(1)#5
O(4)-Na(1)#6
K(1)-O(4)#2
K(1)-O(2)#3
O(2)-K(1)#2
Na(1)-O(1)#5
Na(1)-O(4)#1
O(3)-Na(1)#6
------------
------------
Table 5. Bond angles (deg) around the metal centres for 1a, 2a, 3a, 1b and 2b.
BOND
BOND
BOND
BOND
BOND
2a
3a
1b
2b
ANGLES(°)
ANGLES(°)
ANGLES(°)
ANGLES(°)
ANGLES(°)
O(3)-Li(1)-O(4)#1
O(3)-Li(1)-O(3)#2
109.57(14)
113.88(14)
O(4)#1-Na(1)-O(4)#2
O(4)#1-Na(1)-O(3)#3
180.0
95.00(3)
O(4)#1-K(1)-O(4)
O(4)#1-K(1)-O(3)
89.23(3)
129.53(3)
O(8)#1-Li(1)-O(9)
O(8)#1-Li(1)-O(4)
106.43(12)
112.11(12)
O(4)#1-Na(1)-O(4)#2
O(4)#1-Na(1)-O(3)#3
180.00(7)
95.92(4)
O(4)#1-Li(1)-O(3)#2
O(3)-Li(1)-O(1)#3
111.96(16)
103.92(15)
110.66(14)
106.51(14)
133.08(16)
74.62(9)
O(4)#2-Na(1)-O(3)#3
O(4)#1-Na(1)-O(3)
O(4)#2-Na(1)-O(3)
O(3)#3-Na(1)-O(3)
O(4)#1-Na(1)-O(1)#4
O(4)#2-Na(1)-O(1)#4
O(3)#3-Na(1)-O(1)#4
O(3)-Na(1)-O(1)#4
O(4)#1-Na(1)-O(1)#5
O(4)#2-Na(1)-O(1)#5
85.00(3)
85.00(3)
95.00(3)
180.00(3)
102.50(3)
77.50(3)
90.87(3)
89.13(3)
77.50(3)
102.50(3)
O(4)-K(1)-O(3)
O(4)#1-K(1)-
87.00(3)
89.37(4)
132.82(3)
127.75(3)
82.77(3)
137.88(3)
67.68(3)
88.55(3)
147.96(4)
118.76(4)
O(9)-Li(1)-O(4)
O(8)#1-Li(1)-O(5)
O(9)-Li(1)-O(5)
O(4)-Li(1)-O(5)
------------
115.59(12)
115.47(12)
111.38(12)
95.98(11)
------------
------------
------------
------------
------------
------------
O(4)#2-Na(1)-O(3)#3
O(4)#1-Na(1)-O(3)#4
O(4)#2-Na(1)-O(3)#4
O(3)#3-Na(1)-O(3)#4
O(4)#1-Na(1)-O(1)
O(4)#2-Na(1)-O(1)
O(3)#3-Na(1)-O(1)
O(3)#4-Na(1)-O(1)
O(4)#1-Na(1)-O(1)#5
O(4)#2-Na(1)-O(1)#5
84.08(4)
84.08(4)
95.92(4)
180.0
O(3)#2
O(4)#1-Li(1)-O(1)#3
O(3)#2-Li(1)-O(1)#3
O(3)-Li(1)-Li(1)#2
O(4)#1-Li(1)-Li(1)#2
O(3)#2-Li(1)-Li(1)#2
O(1)#3-Li(1)-Li(1)#2
O(3)-Li(1)-Li(1)#4
O(4)#1-Li(1)-Li(1)#4
O(4)-K(1)-O(3)#2
O(3)-K(1)-O(3)#2
O(4)#1-K(1)-O(2)
O(4)-K(1)-O(2)
O(3)-K(1)-O(2)
O(3)#2-K(1)-O(2)
O(4)#1-K(1)-
79.82(5)
100.18(5)
94.63(4)
85.37(4)
100.18(5)
79.82(5)
------------
37.50(10)
118.49(15)
37.70(4)
------------
------------
------------
O(4)#2
136.81(17)
O(4)-K(1)-O(4)#2
------------

3.3. Thermal stability studies
Thermal analysis curves of all studied compounds are shown in Fig. 6. The thermo
analytical data is summarized in Table 6. The thermal analyses of compound 1a does not
show any weight loss up to 230°C indicating the absence of any coordinated or lattice
water molecules in the complex.[44] Its thermal degradation occurred in two steps. These
two steps in the range of temperature 230-470°C & 470-805°C showed the decomposition
of NPG. [45] These two stages are in connection with a weight loss of 90.90%. The
calculated weight loss value in these two stages is 92.85%. The total observed weight loss
value is 90.90% with a residue equal 9.1% which is corresponding to lithium oxide
Li2O.[46] These results show good agreement with the theoretical values of total loss
equal 92.85% and residual 7.11%.
Table 6. Thermal data of compounds 1a, 2a, 3a, 1b and 2b.
Thermogravimetry(TG)
Temp.
Compounds/ Number of
Tmax. (oC)
Decomposition
Species
Mass Loss
(%)
calculated
range
(oC)
Mass Loss (%)
Observed
Codes
Stages
230-470 426 (-)
470-805 709(-)
40.45
50.32
3.107
1a
2
90.90
92.85
7.71
NPG
60-115
80(+)
7.057
82.41
2H2O
116-176
177-254
255-345
346-389
390-650
250-350
351-572
573-750
100-140
141-170
171-292
293-400
401-775
200-450
451-790
126(+)
204(+)
308(+)
364(+)
472(-)
313(+)
525(-)
747(-)
118 (+)
155(+)
275(+)
338(-)
642(-)
269(+)
594(-)
3.950
40.337
24.416
8.960
2a
3a
6
3
83.87
2NPG
7.852
40.938
13.896
12.850
4.05
67.68
3.90
65.23
H2O
Phthalic acid
100-140
141-170
171-292
293-400
401-775
0.527
1b
2b
5
2
44.023
25.273
21.62
67.351
21.608
91.44
89.48
92.79
91.43
2NPA

The TG-DTA curves of 2a indicate six step decompositions. Dehydration of two water
molecules is observed endothermally in the first two steps between 60-115°C and 116-
176°C.[47] The rest four stages in the range of 177-650°C showed decomposition of two
NPG. These four stages are in connection with a weight loss of 82.41%. The calculated
weight loss value in these four stages is 83.87%. The total observed weight loss value is
89.47 % with a residue equal 10.53 % corresponds to sodium peroxide. These results
show good agreement with the theoretical values of total weight loss equal to 91.57% and
residual 8.35%.
Fig. 6. TGA curves of compounds 1a, 2a, 3a, 1b and 2b.
The thermal analyses of compound 3a does not show any weight loss up to 250°C
indicating the absence of any coordinated or lattice water molecules in the complex. Its
thermal degradation occurred in three stages in the range from 250-750°C giving
potassium super oxide as a final residue.[48] The total weight loss value was 67.68% with
a final residue 32.3% which is equivalent to the theoretical values 65.23% and 34.77%,
respectively. The TG-DTA curves of 1b indicate five step decompositions. Dehydration
of one water molecules is observed endothermally in the first step between 100-140°C.
The rest four stages range of 141-775°C showed the decomposition of two NPA.[49]

These four stages are in connection with a weight loss of 91.44% and the calculated
weight loss value in these four stages is 92.79%. The total observed weight loss value is
95.53% with a residue equal 4.05% corresponds to lithium oxide Li2O. These results
show good agreement with the theoretical values, total loss equal 96.68% and residual
3.89%. The thermal degradation of 2b occurred in two stages in the range from 200-
450°C and 451-790°C giving sodium peroxide (Na2O2) as a final residue.[48] The total
weight loss value was 89.48% with a final residue 10.52% which is equivalent to the
theoretical values 91.43% and 8.49%, respectively.
3.4. Luminescent Properties
The compounds [Li(NPA)2H2O](1b) and [Na(NPA)2](2b) showed two strong
fluorescence emissions (blue emission maxima) with greater intensity comparative to
their ligand fluorescence emission i.e NPA.[50] While the compounds [Li(NPG)](1a),
[Na(NPG)2]2H2O(2a) showed two weak fluorescence emissions (blue emission maxima)
with less intensity comparative to their ligand fluorescence emission i.e. NPG as shown in
Fig.7.
Fig. 7. Fluorescence spectrum of compounds in 1.0 × 10-3 M in DMSO solution at 25.0 ± 0.1 ºC.

Due to base hydrolysis of NPG for potassium complex [C8H5KO4](3a) [51] ligand based
fluorochrome has been changed showing different shape of emission spectrum as
compared to other compounds. Fluorescence emissions spectra depicted in Fig. 8 and data
is presented in Table 7.
Table 7. Fluorescence data of compounds 1a, 2a, 3a, 1b, 2b NPG and NPA.
Compounds
EX(nm)
EM(nm)
Stoke Shift(nm)
1a
367
367
366
374
368
364
368
415 & 438
411 & 437
414 & 438
413 & 437
417& 438
417 & 438
417 & 439
48 & 71
44 & 70
48 & 72
39 & 63
49 & 70
53 & 74
49 & 71
2a
3a
1b
2b
NPG
NPA
Due to the resemblance in the shapes and positions of fluorescence emission and
excitation pattern of complexes and ligands, it can be decided that the emissions observed
for the complex is neither MLCT (metal-to-ligand charge transfer) nor LMCT (ligand-to-
metal charge transfer) in nature, and can be assumed as the intra-ligand fluorescent
emission. [52] The emission observed in the compounds assigned to the (π→π* & n→π*)
intra-ligand fluorescence. [53] The slight difference in the positions of luminescent peaks
in the compounds may be due to the different coordination modes of ligands.
Conclusion
In this work, new polymeric nature compounds [Li(NPG)], [Na(NPG)2]·2H2O,
[C8H5KO4], [Na(NPA)2] had been synthesized. These compounds are structurally
characterized as thermally stable supramolecular alkali metal coordination polymers. The
compound [Li(NPA)H2O] did not show self-assembly, so it can be regarded as lithium
complex of NPA. Co-ordination geometries along with coordination modes were
discussed. The coordination modes are verified by the utilization of useful information

provided by FTIR and Raman spectroscopies. The thermal stability data showed that the
coordination polymers are stable up to much higher extent. Compounds 1a, 2a, 1b & 2b
showed ligand-based photoluminescence properties while in the 3a, ligand based
fluorochrome has been changed showing different shape of emission spectrum as
compared to other compounds.
Supplementary Information
Crystallographic data (excluding structure factors) for the structures in this paper have
been deposited in the Cambridge Crystallographic Data Centre as supplementary
publication, CCDC Nos. 870359, 870722, 872685, 873800 and 876492 for compounds
1a, 2a, 3a, 1b and 2b respectively. Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (internet) +44
1223 336 033; e-mail: deposit@ccdc.cam.ac.uk). or www at http://www.ccdc.cam.ac.uk].
References
[1] R. Murugavel, V.V. Karambelkar, G. Anantharaman, M.G. Walawalkar, Synthesis, Spectral
Characterization, and Structural Studies of 2-Aminobenzoate Complexes of Divalent Alkaline
Earth Metal Ions: X-ray Crystal Structures of [Ca(2-aba)2(OH2)3]∞,[{Sr(2-aba)2(OH2)2}∞ H2O]∞,
and [Ba(2-aba)2 (OH2)]∞(2-abaH= 2-NH2C6H4COOH), Inorg. Chem. 39 (2000) 1381-1390.
[2] J. Lan, D. Cao, W. Wang, B. Smit, Doping of alkali, alkaline-earth, and transition metals in
covalent-organic frameworks for enhancing CO2 capture by first-principles calculations and
molecular simulations, Acs Nano. 4 (2010) 4225-4237.
[3] J. Huskens, D. A. Torres, Z. Kovacs, J. P. André, C. F. Geraldes, A. D. Sherry, Alkaline earth
metal and lanthanide (III) complexes of ligands based upon 1, 4, 7, 10-tetraazacyclododecane-1,
7-bis (acetic acid), Inorg. Chem. 36 (1997) 1495-1503.

[4] J. Sebastian, K.M. Jinka, R.V. Jasra, Effect of alkali and alkaline earth metal ions on the
catalytic epoxidation of styrene with molecular oxygen using cobalt (II)-exchanged zeolite X, Jo
Catal. 244 (2006) 208-218.
[5] M. Takagi, K. Ueno, Crown compounds as alkali and alkaline earth metal ion selective
chromogenic reagents, Host Guest Complex Chemistry III, Springer. 121(1984) 39-65.
[6] H. Wu, W. Zhou, T. Yildirim, Alkali and alkaline-earth metal amidoboranes: structure,
crystal chemistry, and hydrogen storage properties, J. Am. Chem. Soc. 130 (2008) 14834-14839.
[7] K. M. Fromm, R. D. Bergougnant, Transport properties of solid state crown ether channel
systems, Solid. state. Sci. 9 (2007) 580-587.
[8] K. M. Fromm, Recent advances in the chemistry of clusters and inorganic polymers of alkali
and alkaline earth metal compounds, Chimi. Int. J. Chem. 56 (2002) 676-680.
[9] K. M. Fromm, Coordination polymer networks with S-block metal ions, Coord. Chem. Rev.
252 (2008) 856-885.
[10] R. J. Kuppler, D. J. Timmons, Q. R. Fang, J. R. Li, T. A. Makal, M. D. Young, D. Yuan, D.
Zhao, W. Zhuang, H. C. Zhou, Potential applications of metal-organic frameworks, Coord.
Chem. Rev. 253 (2009) 3042-3066.
[11] M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke, M. O'keeffe, O. M. Yaghi,
Modular chemistry: secondary building units as a basis for the design of highly porous and
robust metal-organic carboxylate frameworks, Acc. Chem. Res. 34 (2001) 319-330.
[12] C. Rao, S. Natarajan, R. Vaidhyanathan, Metal carboxylates with open architectures, Ang.
Chem. Int. Ed. 43 (2004) 1466-1496.
[13] M. P. Suh, Y. E. Cheon, E. Y. Lee, Syntheses and functions of porous
metallosupramolecular networks, Coord. Chem. Rev. 252 (2008) 1007-1026.

[14] M. Yoshizawa, M. Nagao, K. Umemoto, K. Biradha, M. Fujita, S. Sakamoto, K.
Yamaguchi, Side chain-directed assembly of triangular molecular panels into a tetrahedron vs.
open cone, Chem. Commun. 0 (2003) 1808-1809.
[15] G. Dong, P. Ke-liang, D. Chun-ying, H. Cheng, M. Qing-jin, Design and Crystal Structures
of Triple Helicates with Crystallographic Idealized D3 Symmetry: The Role of Side Chain Effect
on Crystal Packing, Inorg. Chem. 41 (2002) 5978-5985.
[16] X. L. Wang, Y. Q. Chen, G. C. Liu, H. Y. Lin, W. Y. Zheng, J. X. Zhang, Assembly of
novel phenanthroline-based cobalt (II) coordination polymers by selecting dicarboxylate ligands
with different spacer length: From 1-D chain to 3-D interpenetrated framework, J. Organomet.
Chem. 694 (2009) 2263-2269.
[17] Y. Liu, Y. Qi, Y. H. Su, F. H. Zhao, Y. X. Che, J. M. Zheng, Five novel cobalt coordination
polymers: effect of metal–ligand ratio and structure characteristics of flexible bis (imidazole)
ligands, CrystEngComm, 12 (2010) 3283-3290.
[18] F. Y. Cui, K. L. Huang, Y. Q. Xu, Z. G. Han, X. Liu, Y. N. Chi, C. W. Hu, Structural
variability of Cd (II) and Co (II) mixed-ligand coordination polymers: effect of ligand isomerism
and metal-to-ligand ratio, CrystEngComm, 11 (2009) 2757-2769.
[19] B. C. Tzeng, H. T. Yeh, T. Y. Chang, G. H. Lee, Novel Coordinated-Solvent Induced
Assembly of Cd (II) Coordination Polymers Containing 4, 4′-Dipyridylsulfide, Cryst. Growth
Des. 9 (2009) 2552-2555.
[20] S. C. Chen, Z. H. Zhang, K. L. Huang, Q. Chen, M. Y. He, A. J. Cui, C. Li, Q. Liu, M. Du,
Solvent-controlled assembly of manganese (II) tetrachloroterephthalates with 1D chain, 2D
layer, and 3D coordination architectures, Cryst. Growth Des. 8 (2008) 3437-3445.

[21] T. Prasad, M. Rajasekharan, Solvent dependent crystallization of isomeric chain
coordination polymers in the Ce-Zn/Cd-dipic system, Cryst. Growth Des. 8 (2008) 1346-1352.
[22] V. Pedireddi, S. Varughese, Solvent-dependent coordination polymers: Cobalt complexes of
3, 5-dinitrobenzoic acid and 3, 5-dinitro-4-methylbenzoic acid with 4, 4'-bipyrdine, Inorg. Chem.
43 (2004) 450-457.
[23] N. P. Chatterton, D. M. Goodgame, D. A. Grachvogel, I. Hussain, A. J. White, D. J.
Williams, Influence of the Counteranion on the Formation of Polymeric Networks by Metal
Complexes of Hexamethylenebis (acetamide), Inorg. Chem. 40 (2001) 312-317.
[24] H. Yoo, H. D. Mai, I. Lee, S. Lee, Alkali‐Metal‐Mediated Frameworks based on Di‐(2,
6‐Pyridinedicarboxyate) Cobalt (II) Species, Eur. J. Inorg. Chem, 31 (2017) 3736-3743.
[25] S. M. Humphrey, R. A. Mole, R. I. Thompson, P. T. Wood, Mixed Alkali Metal/Transition
Metal Coordination Polymers with the Mellitic Acid Hexaanion: 2-Dimensional Hexagonal
Magnetic Nets, Inorg. Chem. 49 (2010) 3441-3448.
[26] L. D. M. Lima, P. Castro, A. L. Machado, C. A. M. Fraga, C. Lugnier, V. L. G. de Moraes,
E. J. Barreiro, Synthesis and anti-inflammatory activity of phthalimide derivatives, designed as
new thalidomide analogues, Bioorganic Med. Chem. 10 (2002) 3067-3073.
[27] N. Barooah, J. B. Baruah, Supramolecular chemistry with phthalimide derivatives, Mini
Rev. Org. Chem. 4 (2007) 292-309.
[28] Y. Chen, L. Deng, Parallel kinetic resolutions of monosubstituted succinic anhydrides
catalyzed by a modified cinchona alkaloid, J. Am. Chem. Soc. 123 (2001) 11302-11303.
[29] M. E. Vázquez, J. B. Blanco, B. Imperiali, Photophysics and biological applications of the
environment-sensitive fluorophore 6-N, N-dimethylamino-2, 3-naphthalimide, J. Am. Chem.
Soc. 127 (2005) 1300-1306.

[30] C. J. McAdam, J. L. Morgan, R. E. Murray, B. H. Robinson, J. Simpson, Synthesis and
fluorescence properties of new enaminenaphthalimides, Aust. J. Chem. 57 (2004) 525-530.
[31] T. Sakamoto, C. Pac, A “Green” Route to Perylene Dyes: Direct Coupling Reactions of 1,
8-Naphthalimide and Related Compounds under Mild Conditions Using a “New” Base Complex
Reagent, t-BuOK/DBN, J. Org Chem, 66 (2001) 94-98.
[32] M. E. Vázquez, D. M. Rothman, B. Imperiali, A new environment-sensitive fluorescent
amino acid for Fmoc-based solid phase peptide synthesis, Org. Biomol. Chem. 2 (2004) 1965-
1966.
[33] S. F. Muhammed, Synthesis and Characterization of Some N-Protected Amino Acid
Complexes, J. Am. Sci, 6 (2010).
[34] R. Antunes, H. Batista, R. Srivastava, G. Thomas, C. Araujo, New Phthalimide derivatives
with potent analgesic activity: II, Bioorg. Med. Chem. Lett. 8 (1998) 3071-3076.
[35] N. Barooah, R. J. Sarma, A. S. Batsanov, J. B. Baruah, N-phthaloylglycinato complexes of
Cobalt, Nickel, Copper and Zinc, Polyhedron. 25 (2006) 17-24.
[36] M. N. Khan, Suggested improvement in the ing-manske procedure and gabriel synthesis of
primary amines: kinetic study on alkaline hydrolysis of N-phthaloylglycine and acid hydrolysis
of N-(o-Carboxybenzoyl) glycine in aqueous organic solvents, J. Org. Chem, 61 (1996) 8063-
8068.
[37] K. Nakamoto, Infrared and Raman spectra of inorganic and coordination compounds, Wiley
Online Library1986.
[38] G. Kumar, M. Srivastava, Spectral and magnetochemical studies of nickel (II) and cobalt
(II) complexes of hippuric acid, Rev Chim Miner. 16 (1979) 14-18.

[39] G. Socrates, Infrared and Raman characteristic group frequencies: tables and charts, John
Wiley & Sons 2001.
[40] G. M. Sheldrick, A short history of SHELX, Acta Crystallogr. Sect. A: Found. Crystallogr.
64 (2007) 112-122.
[41] M. Dinca, J. R. Long, Strong H2 binding and selective gas adsorption within the
microporous coordination solid Mg3(O2C-C10H6-CO2)3, J. Am. Chem. Soc. 127 (2005) 9376-
9377.
[42] J. Krogh-Moe, The crystal structure of lithium diborate, Li2O. 2B2O3, Acta Crystallogra. 15
(1962) 190-193.
[43] M. G. Gardiner, G. R. Hanson, M. J. Henderson, F. C. Lee, C. L. Raston, Paramagnetic Bis
(1, 4-di-tert-butyl-1, 4-diazabutadiene) Adducts of Lithium, Magnesium, and Zinc, Inorganic
Chemistry, 33 (1994) 2456-2461.
[44] O. Yaghi, C. E. Davis, G. Li, H. Li, Selective guest binding by tailored channels in a 3-D
porous zinc (II)-benzenetricarboxylate network, J. Am. Chem. Soc. 119 (1997) 2861-2868.
[45] W. L. Armarego, B. A. Milloy, W. Pendergast, A highly stereospecific synthesis of (R)-and
(S)-[2-2 H 1] glycine, J. Chem. Soc. (1976) 2229-2237.
[46] T. Takahashi, T. Kikuchi, Porosity dependence on thermal diffusivity and thermal
conductivity of lithium oxide Li2O from 200 to 900° C, J. Nucl. Mater. 91 (1980) 93-102.
[47] J. Scheirs, G. Camino, W. Tumiatti, Overview of water evolution during the thermal
degradation of cellulose, Euro. Poly. J, 37 (2001) 933-942.
[48] A. Petrocelli, D. Kraus, The inorganic superoxides, J. Chem. Edu. 40 (1963) 146.
[49] I. Hickman, J. Jonsson, J. Prins, S. Ash, D. Purdie, A. Clouston, E. Powell, Modest weight
loss and physical activity in overweight patients with chronic liver disease results in sustained

improvements in alanine aminotransferase, fasting insulin, and quality of life, Gut. 53 (2004)
413-419.
[50] F. Brun, J. J. Toulme, C. Helene, Interactions of aromatic residues of proteins with nucleic
acids. Fluorescence studies of the binding of oligopeptides containing tryptophan and tyrosine
residues to polynucleotides, Biochemistry. 14 (1975) 558-563.
[51] D. J. Jobe, R. E. Verrall, R. Palepu, V. C. Reinsborough, Fluorescence and conductometric
studies of potassium 2-(p-Toluidinyl) naphthalene-6-sulfonate/Cyclodextrin/Surfactant systems,
J. Phy. Chem. C. 92 (1988) 3582-3586.
[52] X. Meng, H. Hou, G. Li, B. Ye, T. Ge, Y. Fan, Y. Zhu, H. Sakiyama, Tetrametallic
macrocyclic frameworks constructed from ferrocenedicarboxylato and 2, 2′-bipyridine:
synthesis, molecular structures and characteristics, J. Organomet. Chem. 689 (2004) 1218-1229.
[53] Y. M. Cheng, Y. S. Yeh, M. L. Ho, P. T. Chou, P. S. Chen, Y. Chi, Dual room-temperature
fluorescent and phosphorescent emission in 8-quinolinolate osmium (II) carbonyl complexes:
Rationalization and generalization of intersystem crossing dynamics, Inorg. Chem. 44 (2005)
4594-4603.

Research Highlights


Synthesis of five alkali metal coordination compounds has been performed.
Hydrolysis of N-phthaloyl glycine, resulted, the formation of potassium compound with phthalic
acid [C8H5KO4].

Different carboxylate coordination modes η2µ3and η1µ1 η2µ2 with interesting geometries around
alkali metals.


Thermal stability studies of alkali metal coordination compounds have been carried out.
Lithium and sodium compounds of N-phthaloyl-ß-alanine showed two strong fluorescence
emissions enhancement relative to their ligand.