EC-MOFPhase-I A computationally ready database of electrically conductive metal-organic

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EC-MOF/Phase-I: A computationally ready

database of electrically conductive metal-organic

frameworks with high-throughput structural and

electronic properties

Zeyu Zhang, Dylan Valente, Yuliang Shi, Dil K. Limbu, Mohammad R.

Momeni∗†, and Farnaz A. Shakib∗

Department of Chemistry and Environmental Science, New Jersey Institute of Technology,

Newark 07102, NJ United States

E-mail: momeni@njit.edu,shakib@njit.edu

Abstract

The advent of π-stacked layered metal-organic frameworks (MOFs) opened up new

horizons for designing compact MOF-based devices as they oﬀer unique electrical con-

ductivity on top of permanent porosity and exceptionally high surface area. By taking

advantage of the modular nature of these electrically conductive (EC) MOFs, an un-

limited number of materials can be created for applications in electronic devices such as

battery electrodes, supercapacitors, and spintronics. Permutation of structural build-

ing blocks including diﬀerent metal nodes and organic linkers results in new systems

with unprecedented and unexplored physical and chemical properties. With the ul-

timate goal of providing a platform for accelerated materials design and discovery,

here, we lay the foundations towards creation of the ﬁrst comprehensive database of

EC-MOFs with an experimentally guided approach. The ﬁrst phase of this database,

arXiv:2210.17428v1 [cond-mat.mtrl-sci] 31 Oct 2022

coined EC-MOF/Phase-I, is comprised of 1,061 bulk and mono-layer structures built by

all possible combinations of experimentally reported organic linkers, functional groups

and metal nodes. A high-throughput screening (HTS) workﬂow is constructed to im-

plement density functional theory calculations with periodic boundary conditions to

optimize the structures and calculate some of their most signiﬁcantly relevant proper-

ties. Since research and development in the area of EC-MOFs has long been suﬀering

from the lack of appropriate initial crystal structures, all the geometries and prop-

erty data have been made available for the use of the community through the online

platform that is developed in the course of this work. This database provides com-

prehensive physical and chemical data of EC-MOFs as well as convenience of selecting

appropriate materials for speciﬁc applications, thus, accelerating design and discovery

of EC-MOF-based compact devices.

Introduction

In the last two decades, metal-organic frameworks (MOFs) have constituted one of the

fastest growing ﬁelds in chemistry and materials science1with a wide range of applications

in adsorption,2separation3and catalysis4, to name a few.5MOFs are a class of porous

crystalline materials obtained through a process usually referred to as reticular synthesis.6

Selected metal nodes and organic linkers, also called secondary building units (SBUs), are

connected via strong coordination bonds to form ordered and permanently porous architec-

tures.7The modular nature of MOFs provides many opportunities to tailor their physical

and chemical characteristics, which has led to more than 110,000 MOFs reported to date

according to the Cambridge Structural Database (CSD).8Traditional MOFs are mostly

classiﬁed as insulators with wide band gaps, which limits their further utilization in elec-

trical and optical devices.9The discovery of π-stacked layered MOFs, also referred to as

two-dimensional (2D) MOFs, in 2012 opened a new research direction in this area due to

the remarkable electrical conductivity of these materials compared to traditional MOFs.10

As a result, more 2D MOFs are being reported by researchers emphasizing on the excel-

lent electrical conductivity and magnetic properties introducing them as viable candidates

for ﬁeld-eﬀect transistors,11 supercapacitors,12 superconductors,13 spintronics14 and cathode

materials in diﬀerent metal-ion batteries.15 Normally, electrically-conductive (EC) MOFs

contain ortho-substituted organic linkers coordinated to transition metal nodes, forming ex-

tended π-conjugated 2D sheets. Weak van der Waals interactions allow stacking of these

2D sheets to form bulk crystalline materials with one-dimensional channels in the stacking

direction. Layers of synthesized EC-MOFs to date generally contain extended π-conjugated

organic linkers and (usually) early 3d transition metal nodes as building blocks, providing

the necessary paths for charge transport along both in-plane and out-of-plane directions.16

Various building blocks for EC-MOFs are reported in the literature and as mentioned above,

MOFs, in general, can be rationally designed by choosing diﬀerent combinations of organic

linkers and metal node building blocks. However, considering the vast and virtually inﬁnite

chemical space of MOFs, it is extremely labor intensive and time consuming to synthesize all

diﬀerent combinations of building blocks to ﬁnd the best materials for any desired applica-

tion. A more eﬃcient and systematic way is to create a comprehensive database of diﬀerent

classes of MOFs and then screen them for desired applications using high-throughput screen-

ing (HTS) techniques.17 Chung et al.18 created a computation-ready, experimental (CoRE)

MOF database with over 5,000 MOFs based on CSD in 2014. Various other datasets have

evolved from the CoRE MOF database, such as CoRE MOF 2014+DDEC19 where partial

atomic charges were determined for 50% of the reported MOFs using density functional the-

ory (DFT) calculations as well as CoRE MOF 2014-DFT-optimized20 where DFT geometric

relaxation was performed for 879 structures. CoRE MOF database itself was updated in

2019 with the total number of MOFs being increased to 14,000.21 On the other hand, the

Cambridge Crystallographic Data Centre (CCDC) created a MOF subset based on existing

CSD which contains the largest number of experimentally synthesized MOFs to date.22 A

total number of 69,666 MOFs were gathered in this subset after screening the original CSD

based on 7 diﬀerent criteria and removing solvent molecules from the MOF pores. A more

recent work by Rosen et al.23 in 2021 introduced a new database called Quantum MOF

(QMOF) database containing 15,713 MOFs that were successfully optimized and analyzed

by HTS periodic DFT workﬂows.

Not only experimental MOFs are collected in diﬀerent databases, a hypothetical MOF

database is also recently built by Wilmer et al.24 where 137,953 new MOFs were created from

a combination of 102 diﬀerent building blocks. More than 300 candidates were selected with

excellent methane storage capacity. These carefully prepared databases allow selection of

materials with desired properties and performance for speciﬁc applications by fast screening

of hundreds and/or thousands of structures. However, they all exclude or at best partially

include π-stacked layered EC-MOFs since they are a very new class of materials. Considering

the wide potentials of EC-MOFs, it is crucial to ﬁrst build a comprehensive database for them

which will then allow various HTS techniques to be routinely applied in order to accelerate

materials design and discovery. Here, we report the ﬁrst installation of our experimentally-

guided, computationally-ready database of EC-MOFs, coined EC-MOF/Phase-I, containing

1,061 bulk and mono-layer structures. This database is available to the community use via

the developed online platform during the course of this study at https://ec-mof.njit.edu. All

the structures in this database follow a comprehensive naming rule as shown generally and

with an example in Figure 1. This naming rule, which will be fully explained in the next

section, gives enough information to the user about the nature of metal nodes, functional

groups, organic linkers, connectivity between building blocks and type of unit cells. In this

way, the users can easily have access to the desired structure in the database through the

choice of each of these components where they can build and download their structure.

Furthermore, the users not only have access to the crystal structures but also geometric

data and electronic properties obtained using our in-house HTS workﬂow. We will provide

the details about the applied procedure and developed software for building the database

in the next section of this manuscript. In section 3 we will present the results of our HTS

Figure 1: Naming rules used for the structures included in EC-MOF/Phase-I database (left)

and an example of a built NiHITP crystal structure (right).

investigation of the created 1,061 systems. Section 4 outlines future directions for this

research while concluding remarks will be made in section 5.

Computational Developments

EC-MOFs from literature

As mentioned above, reticular chemistry is deﬁned as a process that simple molecular build-

ing blocks are linked by strong coordinative bonds to form extended crystalline architectures

such as those of MOFs.25,25,26 In this work, we ﬁrst performed a thorough literature sur-

vey and summarized all reports on EC-MOFs that have been either synthesized and/or

theoretically investigated (see Supporting Information (SI) section S1 for details). With

the intention of developing a structure creation tool for automatic generation of the initial

crystal structures of EC-MOFs for our database, we initially focused on identifying struc-

tural features that induce the highest electrical conductivity. Accordingly, we restricted

the ﬁrst version of our database to π-stacked EC-MOFs with planar layers and extended

π-conjugation through organic linkers and metal nodes with 2+ oxidation state allowing

for eﬀective d−πconjugation. Notably, Hofmann-type MOFs are excluded from the ﬁrst

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EC-MOF/Phase-I:Acomputationallyreadydatabaseofelectricallyconductivemetal-organicframeworkswithhigh-throughputstructuralandelectronicpropertiesZeyuZhang,DylanValente,YuliangShi,DilK.Limbu,MohammadR.Momeniy,andFarnazA.ShakibDepartmentofChemistryandEnvironmentalScience,NewJerseyInstituteofTechnology...

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